Crystalline forms of ethyl 2-[[3-[[3- chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy] acetate

ABSTRACT

The present invention relates to crystalline forms of ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate, herein after also referred to as “compound of formula (I)”. The invention also relates to a process for the production of these crystalline forms, formulations for plant protection and herbicidal compositions which contain one of these crystalline forms.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is the U.S. national phase of International Application No.PCT/EP2018/080597, filed Nov. 8, 2018, which claims the benefit ofEuropean Patent Application No. 17203844.0, filed on Nov. 27, 2017,incorporated herein by references in its entirety.

The present invention relates to crystalline forms of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,herein after also referred to as “compound of formula (I)”.

The invention also relates to a process for the production of thesecrystalline forms and formulations for plant protection which containone of these crystalline forms The present invention also providesherbicidal compositions comprising at least one of these crystallineforms (component A) and at least one further compound selected from theherbicidal compounds B (component B) and safeners C (component C).

The compound of formula (I) is the herbicidal active substance of theformula (I):

The compound of formula (I) and a general procedure for its productionis known from WO 2017/202768.

For the production of active substances on the industrial scale but alsofor the formulation of active substances, in many cases knowledgeconcerning the possible existence of crystalline modifications (alsodescribed as crystalline forms) or of solvates of the active substancein question, and knowledge of the specific properties of suchmodifications and solvates and of methods for their preparation are ofdecisive importance. A range of active substances can exist in differentcrystalline but also in amorphous modifications. Polymorphism is theterm used in these cases. A polymorph is a solid, crystalline phase of acompound which is characterized by a specific, uniform packing andarrangement of the molecules in the solid.

Different modifications of one and the same active substance cansometimes have different properties, for example differences in thefollowing properties: solubility, vapor pressure, dissolution rate,stability against a phase change into a different modification,stability during grinding, suspension stability, optical and mechanicalproperties, hygroscopicity, crystal form and size, filterability,density, melting point, stability to decomposition, color, chemicalreactivity or biological activity.

The applicant's own attempts to convert the compound of formula (I) intoa crystalline solid by crystallization at first resulted in amorphousproducts or in complex mixtures of different crystal modifications,which could only be handled with difficulty and whose stability againstuncontrolled phase change was unsatisfactory.

It has now surprisingly been found that by suitable processes previouslyunknown crystalline, stable modifications of the compounds of formula(I), which do not display the disadvantages of the amorphous compound offormula (I) are obtained in high purity. These modifications are alsodescribed below as form A, form B, form C and form D.

The terms “pure form A”, “pure form B”, “pure form C”, and “pure form D”should be understood to mean that the proportion of the modification inquestion, based on the total quantity of the compound of formula (I), isat least 90 wt. % and in particular at least 95 wt. %.

The general preparation of the compound of formula (I) can be effectede.g. by reaction of amines of formula (II) with oxazinones of formula(III) in the presence of an acid:

The reaction may in principle be carried out in substance. However,preference is given to reacting the amines of formula (II) with theoxazinones of formula (III) in an organic solvent.

Suitable in principle are all solvents which are capable of dissolvingthe amines of formula (II) and the oxazinones of formula (III) at leastpartly, and preferably fully under reaction conditions.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes, aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene, halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene, ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF), esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile, ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone;alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanoland tert.-butanol, organic acids like formic acid, acetic acid,propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonicacid, camphorsulfonic acid, citric acid, trifluoroacetic acid as well asdipolar aprotic solvents such as sulfolane, dimethylsulfoxide,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),1,3-dimethyl-2-imidazolidinone (DMI), N,N′-dimethylpropylene urea(DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are organic acids as mentioned above.

It is also possible to use mixtures of the solvents mentioned.

As acids an organic acids like hydrochloric acid, hydrobromic acid orsulfuric acid, as well as organic acids like formic acid, acetic acid,propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonicacid, camphorsulfonic acid, citric acid, trifluoroacetic acid, can beused.

The acids are generally employed in equimolar amounts, in excess or, ifappropriate, be used as solvent, however they can also be employed incatalytic amounts.

Amines of formula (II) can be obtained from the corresponding pyridinesof formula (IV):

Within the pyridines of formula (IV), the group “PGN” is a protectedamine substituent selected from the group consisting of N₃, aliphatic oraromatic carbamates, aliphatic or aromatic amides, N—C₁-C₆-alkyl-amines,N-aryl-amines or heteroarylamides.

Preferably PGN is selected from the group consisting of N₃,C₁-C₆-alkyl-O(CO)NH—, C₁-C₆-haloalkyl-O(CO)—NH—,(tri-C₁-C₆-alkyl)-Si—C₁-C₆-alkyl-O(CO)NH—, C₂-C₆-alkenyl-O(CO)NH—,C₃-C₆-alkynyl-O(CO)NH—, C₃-C₆-cycloalkyl-O(CO)NH—,fluorenylmethyl-O(CO)NH—, H(CO)N—, C₁-C₆-alkyl-(CO)—NH—,C₁-C₆-haloalkyl-(CO)—NH—, C₁-C₆-alkyl-NH, di(C₁-C₆-alkyl)-N—,(C₁-C₆-alkyoxy-C₁-C₄-alkyl)NH—, di(C₁-C₆-alkyoxy-C₁-C₄-alkyl)N—,C₂-C₆-alkenyl-NH, di(C₂-C₆-alkenyl)N—,(tri-C₁-C₄-alkyl)-Si—C₁-C₄-alkoxy-C₁-C₄-alkyl-NH—,di[(tri-C₁-C₄-alkyl)-Si—C₁-C₄-alkoxy-C₁-C₄-alkyl]N—,fluorenylmethyl-NH—, di(fluorenylmethyl)N—, N-phthalimide,N-2,3-dimethylmaleimide or N-2,5-dimethylpyrrole, phenyl-O(CO)NH—,phenyl-C₁-C₄-alkyl-O(CO)NH—, phenyl-(CO)NH—, phenyl-C₁-C₆-alkyl-(CO)NH—,pyridyl-(CO)—NH—, ortho-(C₁-C₄-alkoxy)-phenyl-NH,di[ortho-(C₁-C₄-alkoxy)-phenyl]N—, para-(C₁-C₄-alkoxy)-phenyl-NH,di[para-(C₁-C₄-alkoxy)-phenyl]N—, phenyl-C₁-C₄-alkyl-NH—,di(phenyl-C₁-C₄-alkyl)N—, para-(C₁-C₄-alkoxy)-phenyl-C₁-C₄-alkyl-NH,di[para-(C₁-C₄-alkoxy)-phenyl-C₁-C₄-alkyl]N—,

-   -   wherein each phenyl or pyridyl ring can be substituted by one to        three substituents selected from the group consisting of        halogen, CN, NO₂, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylsulfinyl        and C₁-C₄-alkylsulfonyl;        more preferably PGN is selected from the group consisting of        C₁-C₆-alkyl-O(CO)NH—, fluorenylmethyl-O(CO)NH—, H(CO)N—,        C₁-C₆-alkyl-(CO)—NH—, C₁-C₆-haloalkyl-(CO)—NH, N-phthalimide,        phenyl-O(CO)NH—, phenyl-C₁-C₄-alkyl-O(CO)NH—,        phenyl-C₁-C₄-alkyl-NH—, di(phenyl-C₁-C₄-alkyl)N—,    -   wherein each phenyl or pyridyl ring can be substituted by one to        three C₁-C₄-alkoxy substituents.

In case “PGN” is an azide substituent, the pyridines of formula (IV) canbe converted into the amine of formula (II) using reductive reactionconditions, such as zinc in an aqueous ammonium chloride solution.

In case “PGN” is an acylated amine substituent, the pyridines of formula(IV) can be converted into the amines of formula (II) using acid.

The use and choice of the “PGN” substituent and appropriate deprotectionmethods will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 4th ed.; Wiley: New York, 2007).

Oxazinones of formula (III) are commercially available or can beprepared by known methods (WO 2000/049002).

Pyridines of formula (IV) can be prepared by reaction of compounds offormula (V) with compounds of formula (VI) in the presence of a base:

Within the compounds of formula (V), L¹ is a leaving group such halogen,C₁-C₆-alkylsulfonate or arylsulfonate; preferably F, Cl,C₁-C₆-alkylsulfonate or arylsulfonate; especially preferred F, Cl,mesylat or tosylat; more preferred F or Cl.

Within the compounds of formulae (IV) and (V), the group “PGN” is aprotected amine substituent as defined above for the amines of formula(II).

The reaction may in principle be carried out in substance. However,preference is given to reacting the compounds of formula (V) with thecompounds of formula (VI) in an organic solvent.

Suitable in principle are all solvents which are capable of dissolvingthe compounds of formula (V) and the compounds of formula (VII) at leastpartly and preferably fully under reaction conditions.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes, aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene, halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene, ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF), esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile, ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; as wellas dipolar aprotic solvents such as sulfolane, dimethylsulfoxide,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),1,3-dimethyl-2-imidazolidinone (DMI), N,N′-dimethylpropylene urea(DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are ethers, nitriles, ketones and dipolar aproticsolvents as mentioned above.

More preferred solvents are ethers and dipolar aprotic solvents asmentioned above.

It is also possible to use mixtures of the solvents mentioned.

Examples of suitable bases include metal-containing bases andnitrogen-containing bases.

Examples of suitable metal-containing bases are inorganic compounds suchas alkali metal and alkaline earth metal hydroxides, and other metalhydroxides, such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, magnesium hydroxide, calcium hydroxide and aluminumhydroxide; alkali metal and alkaline earth metal oxide, and other metaloxides, such as lithium oxide, sodium oxide, potassium oxide, magnesiumoxide, calcium oxide and magnesium oxide, iron oxide, silver oxide;alkali metal and alkaline earth metal hydrides such as lithium hydride,sodium hydride, potassium hydride and calcium hydride, alkali metalamides such as lithium amide, sodium amide and potassium amide, alkalimetal and alkaline earth metal carbonates such as lithium carbonate,sodium carbonate, potassium carbonate, magnesium carbonate, and calciumcarbonate, as well as alkali metal hydrogen carbonates (bicarbonates)such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassiumhydrogen carbonate; alkali metal and alkaline earth metal phosphatessuch as potassium phosphate, calcium phosphate; metal organic compounds,preferably alkali metal alkyls such as methyl lithium, butyl lithium andphenyl lithium, alkyl magnesium halides such as methyl magnesiumchloride as well as alkali metal and alkaline earth metal alkoxides suchas sodium methoxide, sodium ethoxide, potassium ethoxide, potassiumtert-butoxide, potassium tert-pentoxide and dimethoxymagnesium; andfurthermore organic bases, such as tertiary amines such astrimethylamine, triethylamine, diisopropylethylamine andN-methylpiperidine, pyridine, substituted pyridines such as collidinge,lutidine, N-methylmorpholine and 4-dimethylaminopyridine and alsobicyclic amines.

Examples of suitable nitrogen-containing bases are C₁-C₆-alkylamines,preferably trialkylamines, for example triethylamine, trimethylamine,N-ethyldiisopropylamine; ammonia, pyridine, lutidine, collidine,4-(dimethylamino)pyridine (DMAP), imidazole,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

Preferred bases are alkali metal and alkaline earth metal hydrides,alkali metal and alkaline earth metal carbonates, as well as alkalimetal hydrogen carbonates (bicarbonates); alkali metal and alkalineearth metal phosphates; metal organic compounds, alkyl magnesium halidesas well as alkali metal and alkaline earth metal alkoxides; andfurthermore organic bases, such as tertiary amines, pyridine,substituted pyridines and also bicyclic amines.

Especially preferred bases are alkali metal and alkaline earth metalcarbonates, metal organic compounds, alkyl magnesium halides as well asalkali metal and alkaline earth metal alkoxides; and furthermore organicbases, such as tertiary amines, pyridine, substituted pyridines and alsobicyclic amines.

The term base as used herein also includes mixtures of two or more,preferably two of the above compounds. Particular preference is given tothe use of one base.

The bases are generally employed in equimolar amounts or in excess;however they can also be employed as solvent, or, if appropriate, incatalytic amounts.

The bases are generally used in excess, more preferably with from 1 to20 mole equivalents based on the compound of formula (VI), and they mayalso be used as the solvent.

Preferably, the bases are used at from 1 to 5 mole equivalents, verypreferably at from 1 to 3 mole equivalents, more preferably at 1 to 2mole equivalents, based on the compound of formula (VI).

It may be advantageous to add the base offset over a period of time.

The compounds of formula (VI) are commercially available or can beprepared by known methods (e.g. WO 02/098227 or WO 07/083090).

The compounds of formula (V) required for the preparation of pyridinesof formula (XXII) are commercially available or can be prepared by knownmethods from the corresponding amine XV (e.g. Greene, T. W.; Wuts, P. G.M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: New York,2007).

Accordingly, a first object of the present invention relates to thecrystalline form A of the compound of formula (I). Also an object is acompound of formula (I) which at least 90 wt. %, in particular at least95% consists of the crystalline form A.

The form A according to the invention can be identified by X-ray powderdiffractometry on the basis of its diffraction diagram. Thus an X-raypowder diffraction diagram recorded using Cu-Kα radiation (1.54178 Å) at25° C. shows at least 3, often at least 5, in particular at least 7, andespecially all of the reflections quoted in the following table as ° 2θvalues or as interplanar spacings d:

° 2θ  4.7 ± 0.2  7.5 ± 0.2  9.5 ± 0.2 12.2 ± 0.2 12.9 ± 0.2 13.7 ± 0.214.3 ± 0.2 14.5 ± 0.2 19.3 ± 0.2 20.1 ± 0.2 24.7 ± 0.2

Preferably, an X-ray powder diffraction diagram recorded using Cu-Kαradiation (1.54178 Å) at 25° C. shows the following reflections as ° 2θvalues: 4.7±0.2, 7.5±0.2, 9.5±0.2 and 24.7±0.2.

Form A displays a thermogram with a characteristic melting peak in therange from 50 to 80° C. The melting point, determined as the onset ofthe melting peak, typically lies at 60° C. The values quoted here relateto values determined by differential calorimetry (differential scanningcalorimetry, DSC; heating rate 10° C./min).

The production of the form A of the compound of formula (I) according tothe invention is effected by

-   -   by crystallization from a solution of the compound of formula        (I)    -   by crystallization from a solution of the compound of        formula (I) in a suitable organic solvent

The solution of compound of formula (I) can for example be prepared bythe following methods:

-   (1) Dissolution of the compound of formula (I), preferably in a form    different from form A, in one of the solvents mentioned below, or-   (2) Preparation of the compound of formula (I) by a chemical    reaction and transfer of the reaction mixture, if necessary after    removal of reagents and/or side products, into an organic solvent    suitable according to the invention.

For the preparation of the solution by dissolution of the compound offormula (I), essentially any known form of compound of formula (I) canbe used. Often amorphous compound of formula (I) or a mixture ofdifferent crystalline modifications or a mixture of amorphous andcrystalline compound of formula (I) will be used. Also suitable arecrystalline forms of compound of formula (I) and mixtures thereof, forexample the form B according to the invention, the form C describedbelow, and also the form D described below and mixtures of these forms.

The dissolution of the compound of formula (I) is usually effected atroom temperature.

In one embodiment of the invention, the dissolution of the compound offormula (I) is effected at elevated temperature, and naturally thetemperature used for dissolution will not exceed the boiling point ofthe solvent.

The solution of the compound of formula (I) can also be prepared bytransferring a reaction mixture obtained by a chemical reaction, whichcontains the compound of formula (I), if necessary after removal ofreagents and/or side products, into an organic solvent suitableaccording to the invention. This can be effected in such a manner thatthe reaction is performed in an organic solvent or solvent mixture whichconsists at least partly, preferably at least 50 wt. %, of a solventsuitable for the crystallization and, if necessary a workup is performedduring which excess reagents and any catalysts present and anyunsuitable solvents present, for example water and/or methanol, areremoved. The preparation of a solution of the compound of formula (I) bychemical reaction of a suitable precursor of compound of formula (I) canbe effected by analogy to the methods which are described in the stateof the art cited at the beginning, to which full reference is herebymade.

The production of the form A of the compound of formula (I) according tothe invention is effected by crystallization from a solution of thecompound of formula (I) in a suitable organic solvent.

Suitable solvents for the crystallization of form A are aliphatichydrocarbons such as pentane, hexane, cyclohexane, nitromethane andmixtures of C₅-C₈-alkanes, aromatic hydrocarbons such as benzene,chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenatedhydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform,carbon tetrachloride and chlorobenzene, ethers such as diethyl ether,diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole andtetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate;nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone,cyclohexanone; alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol and tert.-butanol, as well as dipolar aproticsolvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide(DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone(DMI), N,N′-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and1-methyl-2 pyrrolidinone (NMP), water, and mixtures of theafore-mentioned solvents.

Preferred solvents are aliphatic hydrocarbons, ethers and alcohols asdescribed above, more preferred alcohols.

In order to obtain form A of the compound of formula (I), thecrystallization is preferably effected at room temperature.

Crystallization of form A is preferably effected under controlledconditions, i.e. the conditions of the crystallization are chosen toachieve a slow crystallization rate.

For this, in a first step i) a solution of the compound of formula (I)in one of the aforesaid organic solvents is prepared, and then in asecond step ii) crystallization of the compound of formula (I) iseffected.

The concentration of compound of formula (I) in the solution used forthe crystallization of form A naturally depends on the nature of thesolvent, the solution temperature and the form of the solved compound offormula (I) (i.e. amorphous or crystalline), and often lies in the rangefrom 5 to 1500 g/l, preferably at 100 g/l. Suitable conditions can bedetermined by the person skilled in the art by routine experiments.

Preferably the solution used for the crystallization contains compoundof formula (I) in a purity of at least 85%, often at least 90%, inparticular at least 95%, i.e. the content of organic impurities whichare not organic solvents is not more than 15 wt. %, often not more than10 wt. %, and in particular not more than 5 wt. %, based on the compoundof formula (I) present dissolved in the solvent.

The solution used for the crystallization is preferably essentially freefrom solvents other than those stated. In this context, “essentiallyfree” means that the concentration of other solvents in the compound offormula (I)-containing solution does not exceed 10 wt. %, often 5 wt. %,based on the total quantity of solvent.

The crystallization of form A of compound of formula (I) can be effectedas follows, for example

-   -   by cooling of the solution which contains the dissolved compound        of formula (I),    -   by allow the solution, which contains the dissolved compound of        formula (I), to stand for some time at room temperature,    -   by addition of a solubility-decreasing solvent to the solution        which contains the dissolved compound of formula (I), in        particular by addition of a nonpolar organic solvent or by        addition of water,    -   by concentration of the solution which contains the dissolved        compound of formula (I),    -   by stirring of a suspension of compound of formula (I) and        preferably seeding with the form A of compound of formula (I),        or    -   by a combination of the aforesaid measures.

The crystallization of form A of compound of formula (I) is preferablyeffected by stirring of a suspension of compound of formula (I).

The crystallization is as a rule carried out until at least 80 wt. %,preferably at least 90 wt. %, of the compound of formula (I) usedcrystallizes out.

If the crystallization of form A is effected by cooling, the coolingrate is preferably less than 10 K/min.

The crystallization of form A can be promoted or accelerated by seedingwith seed crystals of form A, for example by adding seed crystals ofform A before or during the crystallization.

If seed crystals are added during the crystallization, the quantitythereof is typically 0.001 to 10 wt. %, often 0.005 to 5 wt. %, inparticular 0.01 to 1 wt. % and especially 0.05 to 0.5 wt. %, based onthe dissolved compound of formula (I).

If the crystallization is performed in the presence of seed crystals ofform A, these are preferably only added at a temperature at which thesaturation concentration of the compound of formula (I) in the solventin question has been reached, i.e. at or below that temperature at whichthe dissolved quantity of compound of formula (I) forms a saturatedsolution in the solvent in question. The person skilled in the art candetermine the temperature dependence of the saturation concentration ina solvent in routine experiments.

Alternatively, the crystallization can also be effected by addition of a“non-solvent” (i.e. a solubility decreasing solvent) e.g. by addition ofa nonpolar solvent or by addition of water, for example from 5 to 60vol. %, in particular 20 to 55 vol. % and especially from 30 to 50 vol.%, based on the volume of the polar organic solvent or solvent mixtureused for dissolution of the compound of formula (I). The addition of thenonpolar solvent or the addition of water are preferably effected over aprolonged period, for example over a period from 10 mins to 3 hrs, inparticular over a period from 20 mins to 2.5 hrs. If the crystallizationof form A is effected by the addition of a “non-solvent”, the additionof the non-solvent is preferably at a slow rate, e.g. less than 10% v/vper minute, based on the volume of the compound of formula (I) solution.Often the addition will be done in such a manner that the nonpolarsolvent or water is added until the discernable onset of thecrystallization and the mixture thus obtained is then left for a time,during which the crystallization of the form A proceeds. If necessary,the mixture can then be cooled for completion of the crystallization.

In particular, the addition of the nonpolar solvent or the addition ofwater and the addition of seed crystals can be combined.

The addition of the nonpolar solvent can be effected in the form of apure nonpolar solvent or in the form of a mixture of a nonpolar solventwith a solvent used for the dissolution. Examples of nonpolar solventsare aliphatic and cycloaliphatic hydrocarbons with preferably 5 to 10 Catoms such as pentane, hexane, cyclopentane, cyclohexane, isohexane,heptane, cycloheptane, octane, decane or mixtures thereof.

The isolation of the form A from the crystallization product, i.e. theseparation of the form A from the mother liquor, is effected by usualtechniques for the separation of solid components from liquids, forexample by filtration, centrifugation or by decantation. As a rule, theisolated solid will be washed, for example with the solvent used for thecrystallization, with water or with a mixture of the organic solventused for the crystallization with water. The washing can be effected inone or more steps, washing with water often being used in the lastwashing step. The washing is typically effected at temperatures below30° C., often below 25° C. and in particular below 20° C., in order tokeep the loss of valuable product as small as possible. Next, the form Aobtained can be dried and then supplied for further processing. Often,however, the moist active substance obtained after washing, inparticular an active substance moist with water, will be supplieddirectly for the further processing.

By means of the crystallization according to the invention, the form Ais obtained with a compound of formula (I) content of as a rule at least90 wt. %, often 94 wt. %, in particular at least 96 wt. %.

The content of form A, based on the total quantity of compound offormula (I), is typically at least 90% and often at least 95% or atleast 96%.

A further object of the present invention relates to the crystallineform B of compound of formula (I). Also an object is a compound offormula (I) which at least 90 wt. %, in particular at least 95% consistsof the crystalline form B.

The form B according to the invention can be identified by X-ray powderdiffractometry on the basis of its diffraction diagram. Thus an X-raypowder diffraction diagram recorded using Cu-Kα radiation (1.54178 Å) at25° C. shows at least 3, often at least 5, in particular at least 7, andespecially all of the reflections quoted in the following table as ° 2θvalues or as interplanar spacings d:

° 2θ  7.1 ± 0.2  9.4 ± 0.2  9.8 ± 0.2 11.6 ± 0.2 13.6 ± 0.2 13.9 ± 0.215.3 ± 0.2 18.3 ± 0.2 19.0 ± 0.2 20.0 ± 0.2 20.8 ± 0.2 21.6 ± 0.2 22.3 ±0.2 24.5 ± 0.2 27.2 ± 0.2

Preferably, an X-ray powder diffraction diagram recorded using Cu-Kαradiation (1.54178 Å) at 25° C. shows the following reflections as ° 2θvalues: 7.1±0.2, 11.6±0.2, 15.3±0.2, 18.3±0.2 and 21.6±0.2.

Form B displays a thermogram with a characteristic melting peak in therange from 80 to 100° C. The melting point, determined as the onset ofthe melting peak, typically lies at 84° C. The values quoted here relateto values determined by differential calorimetry (differential scanningcalorimetry, DSC; heating rate 10° C./min).

The production of the form B of the compound of formula (I) according tothe invention is effected by

-   -   by crystallization from a solution of the compound of formula        (I)    -   by crystallization from a solution of the compound of        formula (I) in a suitable organic solvent

The solution of compound of formula (I) can for example be prepared bythe following methods:

-   (1) Dissolution of the compound of formula (I), preferably in a form    different from form B, in one of the solvents mentioned below, or-   (2) Preparation of the compound of formula (I) by a chemical    reaction and transfer of the reaction mixture, if necessary after    removal of reagents and/or side products, into an organic solvent    suitable according to the invention.

For the preparation of the solution by dissolution of the compound offormula (I), essentially any known form of compound of formula (I) canbe used. Often amorphous compound of formula (I) or a mixture ofdifferent crystalline modifications or a mixture of amorphous andcrystalline compound of formula (I) will be used. Also suitable arecrystalline forms of compound of formula (I) and mixtures thereof, forexample the form A according to the invention, the form C describedbelow, and also the form D described below and mixtures of these forms.

The dissolution of the compound of formula (I) is usually effected atroom temperature. In one embodiment of the invention, the dissolution ofthe compound of formula (I) is effected at elevated temperature, andnaturally the temperature used for dissolution will not exceed theboiling point of the solvent.

The solution of the compound of formula (I) can also be prepared bytransferring a reaction mixture obtained by a chemical reaction, whichcontains the compound of formula (I), if necessary after removal ofreagents and/or side products, into an organic solvent suitableaccording to the invention. This can be effected in such a manner thatthe reaction is performed in an organic solvent or solvent mixture whichconsists at least partly, preferably at least 50 wt. %, of a solventsuitable for the crystallization and, if necessary a workup is performedduring which excess reagents and any catalysts present and anyunsuitable solvents present, for example water and/or methanol, areremoved. The preparation of a solution of the compound of formula (I) bychemical reaction of a suitable precursor of compound of formula (I) canbe effected by analogy to the methods which are described in the stateof the art cited at the beginning, to which full reference is herebymade.

The production of the form B of the compound of formula (I) according tothe invention is effected by crystallization from a solution of thecompound of formula (I) in a suitable organic solvent.

Suitable solvents for the crystallization of form B are aliphatichydrocarbons such as pentane, hexane, cyclohexane, nitromethane andmixtures of C₅-C₈-alkanes, aromatic hydrocarbons such as benzene,chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenatedhydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform,carbon tetrachloride and chlorobenzene, ethers such as diethyl ether,diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole andtetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate;nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone,cyclohexanone; alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol and tert.-butanol, as well as dipolar aproticsolvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide(DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone(DMI), N,N′-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and1-methyl-2 pyrrolidinone (NMP), water, and mixtures of theafore-mentioned solvents.

Preferred solvents are aliphatic hydrocarbons, ethers and alcohols asdescribed above, more preferred alcohols.

In order to obtain form B of the compound of formula (I), thecrystallization is preferably effected at room temperature.

Crystallization of form B is preferably effected under controlledconditions, i.e. the conditions of the crystallization are chosen toachieve a slow crystallization rate.

For this, in a first step i) a solution of the compound of formula (I)in one of the aforesaid organic solvents is prepared, and then in asecond step ii) crystallization of the compound of formula (I) iseffected.

The concentration of compound of formula (I) in the solution used forthe crystallization of form B naturally depends on the nature of thesolvent, the solution temperature and the form of the solved compound offormula (I) (i.e. amorphous or crystalline), and often lies in the rangefrom 5 to 1500 g/l, preferably at 500 to 1500 g/l, especially preferredat 500 to 1500 g/l, more preferred at 1000 to 1200 g/l. Suitableconditions can be determined by the person skilled in the art by routineexperiments.

Preferably the solution used for the crystallization contains compoundof formula (I) in a purity of at least 85%, often at least 90%, inparticular at least 95%, i.e. the content of organic impurities whichare not organic solvents is not more than 15 wt. %, often not more than10 wt. %, and in particular not more than 5 wt. %, based on the compoundof formula (I) present dissolved in the solvent.

The solution used for the crystallization is preferably essentially freefrom solvents other than those stated. In this context, “essentiallyfree” means that the concentration of other solvents in the compound offormula (I)-containing solution does not exceed 10 wt. %, often 5 wt. %,based on the total quantity of solvent.

The crystallization of form B of compound of formula (I) can be effectedas follows, for example

-   -   by cooling of the solution which contains the dissolved compound        of formula (I),    -   by allow the solution, which contains the dissolved compound of        formula (I), to stand for some time at room temperature,    -   by addition of a solubility-decreasing solvent to the solution        which contains the dissolved compound of formula (I), in        particular by addition of a nonpolar organic solvent or by        addition of water,    -   by concentration of the solution which contains the dissolved        compound of formula (I),    -   by stirring of a suspension of compound of formula (I) and        preferably seeding with the form B of compound of formula (I),        or    -   by a combination of the aforesaid measures.

The crystallization of form B of compound of formula (I) is preferablyeffected by stirring of a suspension of compound of formula (I).

The crystallization is as a rule carried out until at least 80 wt. %,preferably at least 90 wt. %, of the compound of formula (I) usedcrystallizes out.

If the crystallization of form B is effected by cooling, the coolingrate is preferably less than 10 K/min.

The crystallization of form B can be promoted or accelerated by seedingwith seed crystals of form B, for example by adding seed crystals ofform B before or during the crystallization.

If seed crystals are added during the crystallization, the quantitythereof is typically 0.001 to 10 wt. %, often 0.005 to 5 wt. %, inparticular 0.01 to 1 wt. % and especially 0.05 to 0.5 wt. %, based onthe dissolved compound of formula (I).

If the crystallization is performed in the presence of seed crystals ofform B, these are preferably only added at a temperature at which thesaturation concentration of the compound of formula (I) in the solventin question has been reached, i.e. at or below that temperature at whichthe dissolved quantity of compound of formula (I) forms a saturatedsolution in the solvent in question. The person skilled in the art candetermine the temperature dependence of the saturation concentration ina solvent in routine experiments.

Alternatively, the crystallization can also be effected by addition of a“non-solvent” (i.e. a solubility decreasing solvent) e.g. by addition ofa nonpolar solvent or by addition of water, for example from 5 to 60vol. %, in particular 20 to 55 vol. % and especially from 30 to 50 vol.%, based on the volume of the polar organic solvent or solvent mixtureused for dissolution of the compound of formula (I). The addition of thenonpolar solvent or the addition of water are preferably effected over aprolonged period, for example over a period from 10 mins to 3 hrs, inparticular over a period from 20 mins to 2.5 hrs. If the crystallizationof form B is effected by the addition of a “non-solvent”, the additionof the non-solvent is preferably at a slow rate, e.g. less than 10% v/vper minute, based on the volume of the compound of formula (I) solution.Often the addition will be done in such a manner that the nonpolarsolvent or water is added until the discernable onset of thecrystallization and the mixture thus obtained is then left for a time,during which the crystallization of the form B proceeds. If necessary,the mixture can then be cooled for completion of the crystallization.

In particular, the addition of the nonpolar solvent or the addition ofwater and the addition of seed crystals can be combined.

The addition of the nonpolar solvent can be effected in the form of apure nonpolar solvent or in the form of a mixture of a nonpolar solventwith a solvent used for the dissolution. Examples of nonpolar solventsare aliphatic and cycloaliphatic hydrocarbons with preferably 5 to 10 Catoms such as pentane, hexane, cyclopentane, cyclohexane, isohexane,heptane, cycloheptane, octane, decane or mixtures thereof.

The isolation of the form B from the crystallization product, i.e. theseparation of the form B from the mother liquor, is effected by usualtechniques for the separation of solid components from liquids, forexample by filtration, centrifugation or by decantation. As a rule, theisolated solid will be washed, for example with the solvent used for thecrystallization, with water or with a mixture of the organic solventused for the crystallization with water. The washing can be effected inone or more steps, washing with water often being used in the lastwashing step. The washing is typically effected at temperatures below30° C., often below 25° C. and in particular below 20° C., in order tokeep the loss of valuable product as small as possible. Next, the form Bobtained can be dried and then supplied for further processing. Often,however, the moist active substance obtained after washing, inparticular an active substance moist with water, will be supplieddirectly for the further processing.

By means of the crystallization according to the invention, the form Bis obtained with a compound of formula (I) content of as a rule at least90 wt. %, often 94 wt. %, in particular at least 96 wt. %.

The content of form B, based on the total quantity of compound offormula (I), is typically at least 90% and often at least 95% or atleast 96%.

A further object of the present invention relates to the crystallineform C of compound of formula (I). Also an object is a compound offormula (I) which at least 90 wt. %, in particular at least 95% consistsof the crystalline form C.

The form C according to the invention can be identified by X-ray powderdiffractometry on the basis of its diffraction diagram. Thus, an X-raypowder diffraction diagram recorded using Cu-Kα radiation (1.54178 Å) at25° C. shows at least 3, often at least 5, in particular at least 7, andespecially all of the reflections quoted in the following table as ° 2θvalues or as interplanar spacings d:

° 2θ 10.6 ± 0.2 12.3 ± 0.2 15.3 ± 0.2 15.8 ± 0.2 18.3 ± 0.2 18.6 ± 0.219.2 ± 0.2 19.9 ± 0.2 20.6 ± 0.2 21.8 ± 0.2 22.6 ± 0.2 24.5 ± 0.2 25.5 ±0.2 26.0 ± 0.2 27.0 ± 0.2 28.3 ± 0.2

Preferably, an X-ray powder diffraction diagram recorded using Cu-Kαradiation (1.54178 Å) at 25° C. shows the following reflections as ° 2θvalues: 15.3±0.2, 15.8±0.2, 18.3±0.2 21.8±0.2 and 22.6±0.2.

Studies on single crystals of form C demonstrate that the underlyingcrystal structure is monoclinic. The unit cell has the space groupP2₁/c. The characteristic data of the crystal structure of form C(determined at 100 K) are compiled in the following table:

Crystallographic Characteristics of Form C

Parameter Form C class monoclinic space group P2₁/c a 14.3338(7) Å b 9.0069(4) Å c 16.6765(8) Å α 90° β 93.343(2)°     Y 90° volume2149.32(18) Å³ Z 4 density (calculated)     1.603 g/cm³ wavelength  1.54178 Å a, b, c = unit cell length α, β, Y = unit cell angle Z =number of molecules in the unit cell

Form C displays a thermogram with a characteristic melting peak in therange from 80 to 105° C. The melting point, determined as the onset ofthe melting peak, typically lies at 87° C. The values quoted here relateto values determined by differential calorimetry (differential scanningcalorimetry, DSC; heating rate 10° C./min).

The production of the form C of the compound of formula (I) according tothe invention is effected by

-   -   by crystallization from a solution of the compound of formula        (I)    -   by crystallization from a solution of the compound of        formula (I) in a suitable organic solvent

The solution of compound of formula (I) can for example be prepared bythe following methods:

-   (1) Dissolution of the compound of formula (I), preferably in a form    different from form C, in one of the solvents mentioned below, or-   (2) Preparation of the compound of formula (I) by a chemical    reaction and transfer of the reaction mixture, if necessary after    removal of reagents and/or side products, into an organic solvent    suitable according to the invention.

For the preparation of the solution by dissolution of the compound offormula (I), essentially any known form of compound of formula (I) canbe used. Often amorphous compound of formula (I) or a mixture ofdifferent crystalline modifications or a mixture of amorphous andcrystalline compound of formula (I) will be used. Also suitable arecrystalline forms of compound of formula (I) and mixtures thereof, forexample the form A and B according to the invention, and also the form Ddescribed below and mixtures of these forms.

The dissolution of the compound of formula (I) is usually effected attemperatures in the range from room temperature to 75° C. In oneembodiment of the invention, the dissolution of the compound of formula(I) is effected at elevated temperature, in particular at 75° C., andnaturally the temperature used for dissolution will not exceed theboiling point of the solvent.

The solution of the compound of formula (I) can also be prepared bytransferring a reaction mixture obtained by a chemical reaction, whichcontains the compound of formula (I), if necessary after removal ofreagents and/or side products, into an organic solvent suitableaccording to the invention. This can be effected in such a manner thatthe reaction is performed in an organic solvent or solvent mixture whichconsists at least partly, preferably at least 50 wt. %, of a solventsuitable for the crystallization and, if necessary a workup is performedduring which excess reagents and any catalysts present and anyunsuitable solvents present, for example water and/or methanol, areremoved. The preparation of a solution of the compound of formula (I) bychemical reaction of a suitable precursor of compound of formula (I) canbe effected by analogy to the methods which are described in the stateof the art cited at the beginning, to which full reference is herebymade.

The production of the form C of the compound of formula (I) according tothe invention is effected by crystallization from a solution of thecompound of formula (I) in a suitable organic solvent.

Suitable solvents for the crystallization of form C are aliphatichydrocarbons such as pentane, hexane, cyclohexane, nitromethane andmixtures of C₅-C₈-alkanes, aromatic hydrocarbons such as benzene,chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenatedhydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform,carbon tetrachloride and chlorobenzene, ethers such as diethyl ether,diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole andtetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate;nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone,cyclohexanone; alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol and tert.-butanol, as well as dipolar aproticsolvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide(DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone(DMI), N,N′-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and1-methyl-2 pyrrolidinone (NMP), water, and mixtures of theafore-mentioned solvents.

Preferred solvents are aliphatic hydrocarbons, aromatic hydrocarbons,esters, ketones and alcohols as described above, more preferredalcohols.

In order to obtain form C of the compound of formula (I), thecrystallization is preferably effected from 75° C. to room temperature,in particular at room temperature. Crystallization of form C ispreferably effected under controlled conditions, i.e. the conditions ofthe crystallization are chosen to achieve a slow crystallization rate.

For this, in a first step i) a solution of the compound of formula (I)in one of the aforesaid organic solvents is prepared, and then in asecond step ii) crystallization of the compound of formula (I) iseffected.

The concentration of compound of formula (I) in the solution used forthe crystallization of form C naturally depends on the nature of thesolvent, the solution temperature and the form of the solved compound offormula (I) (i.e. amorphous or crystalline), and often lies in the rangefrom 5 to 1500 g/l, preferably from 5 to 500 g/l, especially preferredfrom 5 to 150 g/l. Suitable conditions can be determined by the personskilled in the art by routine experiments.

Preferably the solution used for the crystallization contains compoundof formula (I) in a purity of at least 85%, often at least 90%, inparticular at least 95%, i.e. the content of organic impurities whichare not organic solvents is not more than 15 wt. %, often not more than10 wt. %, and in particular not more than 5 wt. %, based on the compoundof formula (I) present dissolved in the solvent.

The solution used for the crystallization is preferably essentially freefrom solvents other than those stated. In this context, “essentiallyfree” means that the concentration of other solvents in the compound offormula (I)-containing solution does not exceed 10 wt. %, often 5 wt. %,based on the total quantity of solvent.

The crystallization of form C of compound of formula (I) can be effectedas follows, for example

-   -   by cooling of the solution which contains the dissolved compound        of formula (I),    -   by allow the solution, which contains the dissolved compound of        formula (I), to stand for some time at room temperature,    -   by addition of a solubility-decreasing solvent to the solution        which contains the dissolved compound of formula (I), in        particular by addition of a nonpolar organic solvent or by        addition of water,    -   by concentration of the solution which contains the dissolved        compound of formula (I),    -   by stirring of a suspension of compound of formula (I) and        preferably seeding with the form A of compound of formula (I),        or    -   by a combination of the aforesaid measures.

The crystallization of form C of compound of formula (I) is preferablyeffected by cooling of the solution which contains the dissolvedcompound of formula (I), by concentration of the solution which containsthe dissolved compound of formula (I) and/or by stirring of a suspensionof compound of formula (I).

The crystallization is as a rule carried out until at least 80 wt. %,preferably at least 90 wt. %, of the compound of formula (I) usedcrystallizes out.

If the crystallization of form C is effected by cooling, the coolingrate is preferably less than 10 K/min.

The crystallization of form C can be promoted or accelerated by seedingwith seed crystals of form C, for example by adding seed crystals ofform C before or during the crystallization.

If seed crystals are added during the crystallization, the quantitythereof is typically 0.001 to 10 wt. %, often 0.005 to 5 wt. %, inparticular 0.01 to 1 wt. % and especially 0.05 to 0.5 wt. %, based onthe dissolved compound of formula (I).

If the crystallization is performed in the presence of seed crystals ofform C, these are preferably only added at a temperature at which thesaturation concentration of the compound of formula (I) in the solventin question has been reached, i.e. at or below that temperature at whichthe dissolved quantity of compound of formula (I) forms a saturatedsolution in the solvent in question. The person skilled in the art candetermine the temperature dependence of the saturation concentration ina solvent in routine experiments.

Alternatively, the crystallization can also be effected by addition of a“non-solvent” (i.e. a solubility decreasing solvent) e.g. by addition ofa nonpolar solvent or by addition of water, for example from 5 to 60vol. %, in particular 20 to 55 vol. % and especially from 30 to 50 vol.%, based on the volume of the polar organic solvent or solvent mixtureused for dissolution of the compound of formula (I). The addition of thenonpolar solvent or the addition of water are preferably effected over aprolonged period, for example over a period from 10 mins to 3 hrs, inparticular over a period from 20 mins to 2.5 hrs. If the crystallizationof form C is effected by the addition of a “non-solvent”, the additionof the non-solvent is preferably at a slow rate, e.g. less than 10% v/vper minute, based on the volume of the compound of formula (I) solution.Often the addition will be done in such a manner that the nonpolarsolvent or water is added until the discernable onset of thecrystallization and the mixture thus obtained is then left for a time,during which the crystallization of the form C proceeds. If necessary,the mixture can then be cooled for completion of the crystallization.

In particular, the addition of the nonpolar solvent or the addition ofwater and the addition of seed crystals can be combined.

The addition of the nonpolar solvent can be effected in the form of apure nonpolar solvent or in the form of a mixture of a nonpolar solventwith a solvent used for the dissolution. Examples of nonpolar solventsare aliphatic and cycloaliphatic hydrocarbons with preferably 5 to 10 Catoms such as pentane, hexane, cyclopentane, cyclohexane, isohexane,heptane, cycloheptane, octane, decane or mixtures thereof.

The isolation of the form C from the crystallization product, i.e. theseparation of the form C from the mother liquor, is effected by usualtechniques for the separation of solid components from liquids, forexample by filtration, centrifugation or by decantation. As a rule, theisolated solid will be washed, for example with the solvent used for thecrystallization, with water or with a mixture of the organic solventused for the crystallization with water. The washing can be effected inone or more steps, washing with water often being used in the lastwashing step. The washing is typically effected at temperatures below30° C., often below 25° C. and in particular below 20° C., in order tokeep the loss of valuable product as small as possible. Next, the form Cobtained can be dried and then supplied for further processing. Often,however, the moist active substance obtained after washing, inparticular an active substance moist with water, will be supplieddirectly for the further processing.

By means of the crystallization according to the invention, the form Cis obtained with a compound of formula (I) content of as a rule at least90 wt. %, often 94 wt. %, in particular at least 96 wt. %.

The content of form C, based on the total quantity of compound offormula (I), is typically at least 90% and often at least 95% or atleast 96%.

A further object of the present invention relates to the crystallineform D of compound of formula (I). Also an object is a compound offormula (I) which at least 90 wt. %, in particular at least 95% consistsof the crystalline form D.

The form D according to the invention can be identified by X-ray powderdiffractometry on the basis of its diffraction diagram. Thus an X-raypowder diffraction diagram recorded using Cu-Kα radiation (1.54178 Å) at25° C. shows at least 3, often at least 5, in particular at least 7, andespecially all of the reflections quoted in the following table as ° 2θvalues or as interplanar spacings d:

° 2θ  5.2 ± 0.2  6.9 ± 0.2 10.4 ± 0.2 14.7 ± 0.2 18.9 ± 0.2 20.1 ± 0.221.6 ± 0.2 22.1 ± 0.2 23.0 ± 0.2 24.7 ± 0.2

Preferably, an X-ray powder diffraction diagram recorded using Cu-Kαradiation (1.54178 Å) at 25° C. shows the following reflections as ° 2θvalues: 5.2±0.2, 6.9±0.2, 10.4±0.2, 20.1±0.2 and 24.7±0.2.

Studies on single crystals of form D demonstrate that the underlyingcrystal structure is monoclinic. The unit cell has the space groupP21/c. The characteristic data of the crystal structure of form C(determined at 100 K) are compiled in the following table:

Crystallographic Characteristics of Form D

Parameter Form D class monoclinic space group P2₁/c a  18.144(2) Å b9.5408(11) Å c  25.953(3) Å α 90° β 106.923(6)°     Y 90° volume 4298.2(9) Å³ Z 8 density (calculated)      1.603 g/cm³ wavelength  1.54178 Å a, b, c = unit cell length α, β, Y = unit cell angle Z =number of molecules in the unit cell

Form D displays a thermogram with a characteristic melting peak in therange from 55 to 80° C. The melting point, determined as the onset ofthe melting peak, typically lies at 67° C. The values quoted here relateto values determined by differential calorimetry (differential scanningcalorimetry, DSC; heating rate 10° C./min).

The production of the form D of the compound of formula (I) according tothe invention is effected by

-   -   by crystallization from a solution of the compound of formula        (I)    -   by crystallization from a solution of the compound of        formula (I) in a suitable organic solvent

The solution of compound of formula (I) can for example be prepared bythe following methods:

-   (1) Dissolution of the compound of formula (I), preferably in a form    different from form D, in one of the solvents mentioned below, or-   (2) Preparation of the compound of formula (I) by a chemical    reaction and transfer of the reaction mixture, if necessary after    removal of reagents and/or side products, into an organic solvent    suitable according to the invention.

For the preparation of the solution by dissolution of the compound offormula (I), essentially any known form of compound of formula (I) canbe used. Often amorphous compound of formula (I) or a mixture ofdifferent crystalline modifications or a mixture of amorphous andcrystalline compound of formula (I) will be used. Also suitable arecrystalline forms of compound of formula (I) and mixtures thereof, forexample the forms A, B and C according to the invention, and alsomixtures of these forms.

The dissolution of the compound of formula (I) is usually effected atroom temperature. In one embodiment of the invention, the dissolution ofthe compound of formula (I) is effected at elevated temperature, andnaturally the temperature used for dissolution will not exceed theboiling point of the solvent.

The solution of the compound of formula (I) can also be prepared bytransferring a reaction mixture obtained by a chemical reaction, whichcontains the compound of formula (I), if necessary after removal ofreagents and/or side products, into an organic solvent suitableaccording to the invention. This can be effected in such a manner thatthe reaction is performed in an organic solvent or solvent mixture whichconsists at least partly, preferably at least 50 wt. %, of a solventsuitable for the crystallization and, if necessary a workup is performedduring which excess reagents and any catalysts present and anyunsuitable solvents present, for example water and/or methanol, areremoved. The preparation of a solution of the compound of formula (I) bychemical reaction of a suitable precursor of compound of formula (I) canbe effected by analogy to the methods which are described in the stateof the art cited at the beginning, to which full reference is herebymade.

The production of the form D of the compound of formula (I) according tothe invention is effected by crystallization from a solution of thecompound of formula (I) in a suitable organic solvent.

Suitable solvents for the crystallization of form D are aliphatichydrocarbons such as pentane, hexane, cyclohexane, nitromethane andmixtures of C₅-C₈-alkanes, aromatic hydrocarbons such as benzene,chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenatedhydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform,carbon tetrachloride and chlorobenzene, ethers such as diethyl ether,diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole andtetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate;nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone,cyclohexanone; alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol and tert.-butanol, as well as dipolar aproticsolvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide(DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone(DMI), N,N′-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and1-methyl-2 pyrrolidinone (NMP), water, and mixtures of theafore-mentioned solvents.

Preferred solvents are aliphatic hydrocarbons, aromatic hydrocarbons andalcohols as described above, more preferred alcohols.

In order to obtain form D of the compound of formula (I), thecrystallization is preferably effected room temperature.

Crystallization of form D is preferably effected under controlledconditions, i.e. the conditions of the crystallization are chosen toachieve a slow crystallization rate.

For this, in a first step i) a solution of the compound of formula (I)in one of the aforesaid organic solvents is prepared, and then in asecond step ii) crystallization of the compound of formula (I) iseffected.

The concentration of compound of formula (I) in the solution used forthe crystallization of form D naturally depends on the nature of thesolvent, the solution temperature and the form of the solved compound offormula (I) (i.e. amorphous or crystalline), and often lies in the rangefrom 5 to 1500 g/l, preferably from 20 to 500 g/l, especially preferredfrom 25 to 160 g/l. Suitable conditions can be determined by the personskilled in the art by routine experiments.

Preferably the solution used for the crystallization contains compoundof formula (I) in a purity of at least 85%, often at least 90%, inparticular at least 95%, i.e. the content of organic impurities whichare not organic solvents is not more than 15 wt. %, often not more than10 wt. %, and in particular not more than 5 wt. %, based on the compoundof formula (I) present dissolved in the solvent.

The solution used for the crystallization is preferably essentially freefrom solvents other than those stated. In this context, “essentiallyfree” means that the concentration of other solvents in the compound offormula (I)-containing solution does not exceed 10 wt. %, often 5 wt. %,based on the total quantity of solvent.

The crystallization of form D of compound of formula (I) can be effectedas follows, for example

-   -   by cooling of the solution which contains the dissolved compound        of formula (I),    -   by allow the solution, which contains the dissolved compound of        formula (I), to stand for some time at room temperature,    -   by addition of a solubility-decreasing solvent to the solution        which contains the dissolved compound of formula (I), in        particular by addition of a nonpolar organic solvent or by        addition of water,    -   by concentration of the solution which contains the dissolved        compound of formula (I),    -   by stirring of a suspension of compound of formula (I) and        preferably seeding with the form A of compound of formula (I),        or    -   by a combination of the aforesaid measures.

The crystallization of form D of compound of formula (I) is preferablyeffected by concentration of the solution which contains the dissolvedcompound of formula (I) and/or by stirring of a suspension of compoundof formula (I).

The crystallization is as a rule carried out until at least 80 wt. %,preferably at least 90 wt. %, of the compound of formula (I) usedcrystallizes out.

If the crystallization of form D is effected by cooling, the coolingrate is preferably less than 10 K/min.

The crystallization of form D can be promoted or accelerated by seedingwith seed crystals of form D, for example by adding seed crystals ofform D before or during the crystallization.

If seed crystals are added during the crystallization, the quantitythereof is typically 0.001 to 10 wt. %, often 0.005 to 5 wt. %, inparticular 0.01 to 1 wt. % and especially 0.05 to 0.5 wt. %, based onthe dissolved compound of formula (I).

If the crystallization is performed in the presence of seed crystals ofform D, these are preferably only added at a temperature at which thesaturation concentration of the compound of formula (I) in the solventin question has been reached, i.e. at or below that temperature at whichthe dissolved quantity of compound of formula (I) forms a saturatedsolution in the solvent in question. The person skilled in the art candetermine the temperature dependence of the saturation concentration ina solvent in routine experiments.

Alternatively, the crystallization can also be effected by addition of a“non-solvent” (i.e. a solubility decreasing solvent) e.g. by addition ofa nonpolar solvent or by addition of water, for example from 5 to 60vol. %, in particular 20 to 55 vol. % and especially from 30 to 50 vol.%, based on the volume of the polar organic solvent or solvent mixtureused for dissolution of the compound of formula (I). The addition of thenonpolar solvent or the addition of water are preferably effected over aprolonged period, for example over a period from 10 mins to 3 hrs, inparticular over a period from 20 mins to 2.5 hrs. If the crystallizationof form D is effected by the addition of a “non-solvent”, the additionof the non-solvent is preferably at a slow rate, e.g. less than 10% v/vper minute, based on the volume of the compound of formula (I) solution.Often the addition will be done in such a manner that the nonpolarsolvent or water is added until the discernable onset of thecrystallization and the mixture thus obtained is then left for a time,during which the crystallization of the form D proceeds. If necessary,the mixture can then be cooled for completion of the crystallization.

In particular, the addition of the nonpolar solvent or the addition ofwater and the addition of seed crystals can be combined.

The addition of the nonpolar solvent can be effected in the form of apure nonpolar solvent or in the form of a mixture of a nonpolar solventwith a solvent used for the dissolution. Examples of nonpolar solventsare aliphatic and cycloaliphatic hydrocarbons with preferably 5 to 10 Catoms such as pentane, hexane, cyclopentane, cyclohexane, isohexane,heptane, cycloheptane, octane, decane or mixtures thereof.

The isolation of the form D from the crystallization product, i.e. theseparation of the form D from the mother liquor, is effected by usualtechniques for the separation of solid components from liquids, forexample by filtration, centrifugation or by decantation. As a rule, theisolated solid will be washed, for example with the solvent used for thecrystallization, with water or with a mixture of the organic solventused for the crystallization with water. The washing can be effected inone or more steps, washing with water often being used in the lastwashing step. The washing is typically effected at temperatures below30° C., often below 25° C. and in particular below 20° C., in order tokeep the loss of valuable product as small as possible. Next, the form Dobtained can be dried and then supplied for further processing. Often,however, the moist active substance obtained after washing, inparticular an active substance moist with water, will be supplieddirectly for the further processing.

By means of the crystallization according to the invention, the form Dis obtained with a compound of formula (I) content of as a rule at least90 wt. %, often 94 wt. %, in particular at least 96 wt. %.

The content of form D, based on the total quantity of compound offormula (I), is typically at least 90% and often at least 95% or atleast 96%.

The forms A, B, C and/or D, preferably form C, of compound of formula(I) are suitable as herbicides.

The invention thus also relates to plant protection agents containingthe forms A, B, C and/or D, preferably form C and additives usual forthe formulation of plant protection agents, in particular plantprotection agents in the form of aqueous suspension concentrates(so-called SC's) or non-aqueous suspension concentrates (so-calledOD's), and plant protection agents in the form of powders (so-calledWP's) and granules (so-called WG's) dispersible in water. The inventionalso relates to a process for combating undesired plant growth, which ischaracterized in that the forms A, B, C and/or D, preferably form C, ofcompound of formula (I), preferably as a suitable active substancepreparation, is used on plants, their habitat and/or on seeds.

The plant protection agents which contain compound of formula (I) in theforms A, B, C and/or D, preferably form C, combat plant growth, inparticular monocotyledonous weed species such as Avena, Lolium,Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria, Cyperus species,Agropyron, Cynodon, Imparato and Sorghum, and dicotyledonous weedspecies such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus,Sinapsis, Ipomoea, Matricaria, Abutilon, Sida, Convolvulus, Cirsium,Rumex and Artemisia on non-cultivated areas very well, particularly athigh application levels.

Depending on the particular application method, the forms A, B, C and/orD, preferably form C, of compound of formula (I) or the plant protectionagents containing them can also be used in a further number of cropplants for the elimination of undesired plants.

Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa,Brassica napus var. napus, Brassica napus var. napobrassica, Brassicarapa var. silvestris, Brassica oleracea, Brassica nigra, Camelliasinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon,Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica),Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis,Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum,Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Heveabrasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglansregia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum,Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotianatabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus,Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisumsativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca,Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre,Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba,Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao,Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Viciafaba, Vitis vinifera and Zea mays.

Preferred crops are Arachis hypogaea, Beta vulgaris spec. altissima,Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrussinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodondactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum,Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeumvulgare, Juglans regia, Lens culinaris, Linum usitatissimum,Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotianatabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus,Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus dulcis,Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghumbicolor (S. vulgare), Triticale, Triticum aestivum, Triticum durum,Vicia faba, Vitis vinifera and Zea mays.

Especially preferred crops are crops of cereals, corn, soybeans, rice,oilseed rape, cotton, potatoes, peanuts or permanent crops.

The forms A, B, C and/or D, preferably form C, of compound of formula(I) according to the invention, or the agrochemical compositions and/orherbicidal compositions comprising the aforementioned forms, can also beused in crops which have been modified by mutagenesis or geneticengineering in order to provide a new trait to a plant or to modify analready present trait.

The term “crops” as used herein includes also (crop) plants which havebeen modified by mutagenesis or genetic engineering in order to providea new trait to a plant or to modify an already present trait.

Mutagenesis includes techniques of random mutagenesis using X-rays ormutagenic chemicals, but also techniques of targeted mutagenesis, inorder to create mutations at a specific locus of a plant genome.Targeted mutagenesis techniques frequently use oligonucleotides orproteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleasesto achieve the targeting effect.

Genetic engineering usually uses recombinant DNA techniques to createmodifications in a plant genome which under natural circumstances cannotreadily be obtained by cross breeding, mutagenesis or naturalrecombination. Typically, one or more genes are integrated into thegenome of a plant in order to add a trait or improve a trait. Theseintegrated genes are also referred to as transgenes in the art, whileplant comprising such transgenes are referred to as transgenic plants.The process of plant transformation usually produces severaltransformation events, which differ in the genomic locus in which atransgene has been integrated. Plants comprising a specific transgene ona specific genomic locus are usually described as comprising a specific“event”, which is referred to by a specific event name. Traits whichhave been introduced in plants or have been modified include inparticular herbicide tolerance, insect resistance, increased yield andtolerance to abiotic conditions, like drought.

Herbicide tolerance has been created by using mutagenesis as well asusing genetic engineering. Plants which have been rendered tolerant toacetolactate synthase (ALS) inhibitor herbicides by conventional methodsof mutagenesis and breeding comprise plant varieties commerciallyavailable under the name Clearfield®. However, most of the herbicidetolerance traits have been created via the use of transgenes.

Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D,dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylureaherbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvatedioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.

Transgenes which have been used to provide herbicide tolerance traitscomprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5,mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance toglufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, fortolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, fortolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA,for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPDinhibitor herbicides: hppdPF, W336 and avhppd-03.

Transgenic corn events comprising herbicide tolerance genes are forexample, but not excluding others, DAS40278, MON801, MON802, MON809,MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603,GA21, MZHGOJG, HCEM485, VCO-Ø1981-5, 676, 678, 680, 33121, 4114, 59122,98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25,TC1507 and TC6275.

Transgenic soybean events comprising herbicide tolerance genes are forexample, but not excluding others, GTS 40-3-2, MON87705, MON87708,MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35,DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTØH2, W62, W98,FG72 and CV127.

Transgenic cotton events comprising herbicide tolerance genes are forexample, but not excluding others, 19-51a, 31707, 42317, 81910,281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224,MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3and T304-40.

Transgenic canola events comprising herbicide tolerance genes are forexample, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92,MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

Insect resistance has mainly been created by transferring bacterialgenes for insecticidal proteins to plants. Transgenes which have mostfrequently been used are toxin genes of Bacillus spec. and syntheticvariants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105,cry1F, crylFa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1,cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant originhave been transferred to other plants. In particular genes coding forprotease inhibitors, like CpTI and pinII. A further approach usestransgenes in order to produce double stranded RNA in plants to targetand downregulate insect genes. An example for such a transgene isdvsnf7.

Transgenic corn events comprising genes for insecticidal proteins ordouble stranded RNA are for example, but not excluding others, Bt10,Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017,MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162,DBT418 and MZIR098.

Transgenic soybean events comprising genes for insecticidal proteins arefor example, but not excluding others, MON87701, MON87751 and DAS-81419.

Transgenic cotton events comprising genes for insecticidal proteins arefor example, but not excluding others, SGK321, MON531, MON757, MON1076,MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B,COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236,3006-210-23, GHB119 and SGK321.

Increased yield has been created by increasing ear biomass using thetransgene athb17, being present in corn event MON87403, or by enhancingphotosynthesis using the transgene bbx32, being present in the soybeanevent MON87712.

Crops comprising a modified oil content have been created by using thetransgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybeanevents comprising at least one of these genes are: 260-05, MON87705 andMON87769.

Tolerance to abiotic conditions, in particular to tolerance to drought,has been created by using the transgene cspB, comprised by the cornevent MON87460 and by using the transgene Hahb-4, comprised by soybeanevent IND-ØØ41Ø-5.

Traits are frequently combined by combining genes in a transformationevent or by combining different events during the breeding process.Preferred combination of traits are herbicide tolerance to differentgroups of herbicides, insect tolerance to different kind of insects, inparticular tolerance to lepidopteran and coleopteran insects, herbicidetolerance with one or several types of insect resistance, herbicidetolerance with increased yield as well as a combination of herbicidetolerance and tolerance to abiotic conditions.

Plants comprising singular or stacked traits as well as the genes andevents providing these traits are well known in the art. For example,detailed information as to the mutagenized or integrated genes and therespective events are available from websites of the organizations“International Service for the Acquisition of Agri-biotech Applications(ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center forEnvironmental Risk Assessment (CERA)”(http://cera-gmc.org/GMCropDatabase), as well as in patent applications,like EP3028573 and WO2017/011288.

The use of compositions according to the invention on crops may resultin effects which are specific to a crop comprising a certain gene orevent. These effects might involve changes in growth behavior or changedresistance to biotic or abiotic stress factors. Such effects may inparticular comprise enhanced yield, enhanced resistance or tolerance toinsects, nematodes, fungal, bacterial, mycoplasma, viral or viroidpathogens as well as early vigour, early or delayed ripening, cold orheat tolerance as well as changed amino acid or fatty acid spectrum orcontent.

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of ingredients or newingredients, specifically to improve raw material production, e.g.,potatoes that produce increased amounts of amylopectin (e.g. Amflora®potato, BASF SE, Germany).

The forms A, B, C and/or D, preferably form C, of compound of formula(I) are also just as suitable as the known amorphous compound of formula(I) for the defoliation and desiccation of plant parts, for example forcrop plants such as cotton, potato, rape, sunflower, soya bean or fieldbeans, in particular cotton.

In this regard, embodiments of the invention also relate to agents forthe desiccation and/or defoliation of plants, processes for theproduction of these agents and methods for the desiccation and/ordefoliation of plants using the forms A, B, C and/or D, preferably formC, of the compound of formula (I).

The forms A, B, C and/or D, preferably form C, of the compound offormula (I) are in particular suitable as desiccants for the desiccationof the aboveground parts of crop plants such as potato, oilseed rape,sunflower and soya bean, but also cereals. This enables completelymechanical harvesting of these important crop plants.

Also of scientific interest is the facilitation of harvesting which isenabled by the time-concentrated dropping or reduction of the strengthof attachment to the tree with citrus fruits, olives or other speciesand varieties of pomaceous, stone and shelled fruit. The same mechanism,i.e. the promotion of the formation of separation tissue between fruitor leaf and shoot of the plants is also significant for well-controlleddefoliation of useful plants, in particular cotton.

In addition, the shortening of the time interval in which the individualcotton plants become ripe leads to heightened fiber quality after theharvest.

To widen the spectrum of action and to achieve synergistic effects, theforms A, B, C and/or D, preferably form C, may be mixed with a largenumber of representatives of other herbicidal or growth-regulatingactive ingredient groups and then applied concomitantly. Suitablecomponents for mixtures are, for example, herbicides from the classes ofthe acetamides, amides, aryloxyphenoxypropionates, benzamides,benzofuran, benzoic acids, benzothiadiazinones, bipyridylium,carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones,dinitroanilines, dinitrophenol, diphenyl ether, glycines,imidazolinones, isoxazoles, isoxazolidinones, nitriles,N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides,phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles,phenylpyrazolines, phenylpyridazines, phosphinic acids,phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles,pyridazinones, pyridines, pyridinecarboxylic acids,pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates,quinolinecarboxylic acids, semicarbazones,sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones,thiadiazoles, thiocarbamates, triazines, triazinones, triazoles,triazolinones, triazolocarboxamides, triazolopyrimidines, triketones,uracils, ureas.

It may furthermore be beneficial to apply the forms A, B, C and/or D,preferably form C, alone or in combination with other herbicides, orelse in the form of a mixture with other crop protection agents, forexample together with agents for controlling pests or phytopathogenicfungi or bacteria. Also of interest is the miscibility with mineral saltsolutions, which are employed for treating nutritional and trace elementdeficiencies. Other additives such as non-phytotoxic oils and oilconcentrates may also be added.

In one embodiment of the present invention the compositions according tothe present invention comprise the forms A, B, C and/or D, (componentA), preferably form C (component A), and at least one further activecompound selected from herbicides B, preferably herbicides B of classb1) to b15), and safeners C (compound C, component C).

In another embodiment of the present invention the compositionsaccording to the present invention comprise form the forms A, B, Cand/or D, (component A), preferably form C (component A), and at leastone further active compound B (herbicide B, component B).

The further herbicidal compound B (component B) is preferably selectedfrom the herbicides of class b1) to b15):

B) herbicides of class b1) to b15):

-   -   b1) lipid biosynthesis inhibitors;    -   b2) acetolactate synthase inhibitors (ALS inhibitors);    -   b3) photosynthesis inhibitors;    -   b4) protoporphyrinogen-IX oxidase inhibitors,    -   b5) bleacher herbicides;    -   b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP        inhibitors);    -   b7) glutamine synthetase inhibitors;    -   b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors);    -   b9) mitosis inhibitors;    -   b10) inhibitors of the synthesis of very long chain fatty acids        (VLCFA inhibitors);    -   b11) cellulose biosynthesis inhibitors;    -   b12) decoupler herbicides;    -   b13) auxinic herbicides;    -   b14) auxin transport inhibitors; and    -   b15) other herbicides selected from the group consisting of        bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin,        cumyluron, dalapon, dazomet, difenzoquat,        difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and        its salts, etobenzanid, flamprop, flamprop-isopropyl,        flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl,        flurenol, flurenol-butyl, flurprimidol, fosamine,        fosamine-ammonium, indanofan, indaziflam, maleic hydrazide,        mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide,        methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid,        oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine,        triaziflam, tridiphane and        6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (CAS        499223-49-3) and its salts and esters;        including their agriculturally acceptable salts or derivatives.

Preference is given to those compositions according to the presentinvention comprising at least one herbicide B selected from herbicidesof class b2, b3, b4, b5, b6, b7, b9, b10 and b13.

Specific preference is given to those compositions according to thepresent invention which comprise at least one herbicide B selected fromthe herbicides of class b4, b6, b7, b9, b10 and b13.

Particular preference is given to those compositions according to thepresent invention which comprise at least one herbicide B selected fromthe herbicides of class b4, b6, b10 and b13.

Examples of herbicides B which can be used in combination with the formsA, B, C and/or D, preferably form C, according to the present inventionare:

b1) from the group of the lipid biosynthesis inhibitors:

ACC-herbicides such as alloxydim, alloxydim-sodium, butroxydim,clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop,cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop,fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop,fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop,haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden,profoxydim, propaquizafop, quizalofop, quizalofop-ethyl,quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl,quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim,4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-72-6);4-(2′,4′-Dichloro-4-cyclopropyl[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-45-3);4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1033757-93-5);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione(CAS 1312340-84-3);5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312337-48-6);5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one;5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312340-82-1);5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1033760-55-2);4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312337-51-1);4-(2′,4′-Dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester;4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312340-83-2);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicidessuch as benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC,esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate,prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;b2) from the group of the ALS inhibitors:sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron,bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron,cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl,ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron,flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron,halosulfuron-methyl, imazosulfuron, iodosulfuron,iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium,mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl,nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron,primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron,pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl,sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron,tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron,triflusulfuron-methyl and tritosulfuron, imidazolinones such asimazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr,imazaquin and imazethapyr, triazolopyrimidine herbicides andsulfonanilides such as cloransulam, cloransulam-methyl, diclosulam,flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan andpyroxsulam, pyrimidinylbenzoates such as bispyribac, bispyribac-sodium,pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac,pyrithiobac-sodium,4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoicacid-1-methylethyl ester (CAS 420138-41-6),4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoicacid propyl ester (CAS 420138-40-5),N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine(CAS 420138-01-8), sulfonylaminocarbonyl-triazolinone herbicides such asflucarbazone, flucarbazone-sodium, propoxycarbazone,propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; andtriafamone;among these, a preferred embodiment of the invention relates to thosecompositions comprising at least one imidazolinone herbicide;b3) from the group of the photosynthesis inhibitors:amicarbazone, inhibitors of the photosystem II, e.g.1-(6-tert-butylpyrimidin-4-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one(CAS 1654744-66-7),1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one(CAS 1637455-12-9),1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one(CAS 1637453-94-1),1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one(CAS 1654057-29-0),1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one(CAS 1654747-80-4),4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;(CAS 2023785-78-4),4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 2023785-79-5),5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 1701416-69-4),4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 1708087-22-2),4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one(CAS 2023785-80-8),1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one(CAS 1844836-64-1), triazine herbicides, including of chlorotriazine,triazinones, triazindiones, methylthiotriazines and pyridazinones suchas ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, propazine, simazine,simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl ureasuch as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron,fluometuron, isoproturon, isouron, linuron, metamitron,methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon,siduron, tebuthiuron and thiadiazuron, phenyl carbamates such asdesmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrileherbicides such as bromofenoxim, bromoxynil and its salts and esters,ioxynil and its salts and esters, uraciles such as bromacil, lenacil andterbacil, and bentazon and bentazon-sodium, pyridate, pyridafol,pentanochlor and propanil and inhibitors of the photosystem I such asdiquat, diquat-dibromide, paraquat, paraquat-dichloride andparaquat-dimetilsulfate. Among these, a preferred embodiment of theinvention relates to those compositions comprising at least one arylurea herbicide. Among these, likewise a preferred embodiment of theinvention relates to those compositions comprising at least one triazineherbicide. Among these, likewise a preferred embodiment of the inventionrelates to those compositions comprising at least one nitrile herbicide;b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone,benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl,chlomethoxyfen, chlorphthalim, cinidon-ethyl, fluazolate, flufenpyr,flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin,fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl,fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen,pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl,saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin,ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate(CAS 353292-31-6; S-3100),N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 452098-92-9),N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 915396-43-9),N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 452099-05-7),N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 452100-03-7),3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione(CAS 451484-50-7),2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione(CAS 1300118-96-0),1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione(CAS 1304113-05-0), methyl(E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate(CAS 948893-00-3), and3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione(CAS 212754-02-4);b5) from the group of the bleacher herbicides:PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone,flurtamone, norflurazon, picolinafen, and4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)-pyrimidine (CAS180608-33-7), HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone,clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione (CAS1486617-21-3), pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione,tefuryltrione, tembotrione, tolpyralate, topramezone, bleacher, unknowntarget: aclonifen, amitrole flumeturon,2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide(CAS 1361139-71-0),2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidone (CAS81777-95-9) and2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS81778-66-7);b6) from the group of the EPSP synthase inhibitors:glyphosate, glyphosate-isopropylammonium, glyposate-potassium andglyphosate-trimesium (sulfosate);b7) from the group of the glutamine synthase inhibitors:bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-Pand glufosinate-ammonium;b8) from the group of the DHP synthase inhibitors:asulam;b9) from the group of the mitosis inhibitors:compounds of group K1: dinitroanilines such as benfluralin, butralin,dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin,prodiamine and trifluralin, phosphoramidates such as amiprophos,amiprophos-methyl, and butamiphos, benzoic acid herbicides such aschlorthal, chlorthal-dimethyl, pyridines such as dithiopyr andthiazopyr, benzamides such as propyzamide and tebutam; compounds ofgroup K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl,flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham;among these, compounds of group K1, in particular dinitroanilines arepreferred;b10) from the group of the VLCFA inhibitors:chloroacetamides such as acetochlor, alachlor, amidochlor, butachlor,dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor,metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor andthenylchlor, oxyacetanilides such as flufenacet and mefenacet,acetanilides such as diphenamid, naproanilide, napropamide andnapropamide-M, tetrazolinones such fentrazamide, and other herbicidessuch as anilofos, cafenstrole, fenoxasulfone, ipfencarbazone,piperophos, pyroxasulfone and isoxazoline compounds of the formulaeII.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9

-   -   the isoxazoline compounds of the formula (II) are known in the        art, e.g. from WO 2006/024820, WO 2006/037945, WO 2007/071900        and WO 2007/096576;    -   among the VLCFA inhibitors, preference is given to        chloroacetamides and oxyacetamides;        b11) from the group of the cellulose biosynthesis inhibitors:        chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben,        triaziflam and        1-cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine        (CAS 175899-01-1);        b12) from the group of the decoupler herbicides:        dinoseb, dinoterb and DNOC and its salts;        b13) from the group of the auxinic herbicides:        2,4-D and its salts and esters such as clacyfos, 2,4-DB and its        salts and esters, aminocyclopyrachlor and its salts and esters,        aminopyralid and its salts such as        aminopyralid-dimethylammonium,        aminopyralid-tris(2-hydroxypropyl)ammonium and its esters,        benazolin, benazolin-ethyl, chloramben and its salts and esters,        clomeprop, clopyralid and its salts and esters, dicamba and its        salts and esters, dichlorprop and its salts and esters,        dichlorprop-P and its salts and esters, flopyrauxifen,        fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen        and its salts and esters (CAS 943832-60-8); MCPA and its salts        and esters, MCPA-thioethyl, MCPB and its salts and esters,        mecoprop and its salts and esters, mecoprop-P and its salts and        esters, picloram and its salts and esters, quinclorac,        quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and        its salts and esters, florpyrauxifen, florpyrauxifen-benzyl (CAS        1390661-72-9) and        4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic        acid (CAS 1629965-65-6);        b14) from the group of the auxin transport inhibitors:        diflufenzopyr, diflufenzopyr-sodium, naptalam and        naptalam-sodium;        b15) from the group of the other herbicides: bromobutide,        chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron,        cyclopyrimorate (CAS 499223-49-3) and its salts and esters,        dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate,        dimethipin, DSMA, dymron, endothal and its salts, etobenzanid,        flurenol, flurenol-butyl, flurprimidol, fosamine,        fosamine-ammonium, indanofan, maleic hydrazide, mefluidide,        metam, methiozolin (CAS 403640-27-7), methyl azide, methyl        bromide, methyl-dymron, methyl iodide, MSMA, oleic acid,        oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine and        tridiphane.

Preferred herbicides B that can be used in combination with the forms A,B, C and/or D, preferably form C, of the formula (I) according to thepresent invention are:

b1) from the group of the lipid biosynthesis inhibitors:

clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl,diclofop-methyl, fenoxaprop-P-ethyl, fluazifop-P-butyl,haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop,quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim,tralkoxydim,4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-72-6);4-(2′,4′-Dichloro-4-cyclopropyl[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-45-3);4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1033757-93-5);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione(CAS 1312340-84-3);5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312337-48-6);5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one;5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312340-82-1);5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1033760-55-2);4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312337-51-1);4-(2′,4′-Dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester;4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312340-83-2);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1033760-58-5); benfuresate,dimepiperate, EPTC, esprocarb, ethofumesate, molinate, orbencarb,prosulfocarb, thiobencarb and triallate;b2) from the group of the ALS inhibitors:amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium,chlorimuron-ethyl, chlorsulfuron, cloransulam-methyl, cyclosulfamuron,diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron,florasulam, flucarbazone-sodium, flucetosulfuron, flumetsulam,flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl,imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium,iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron,metosulam, metsulfuron-methyl, nicosulfuron, orthosulfamuron,oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium,propyrisulfuron, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim,pyrimisulfan, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium,pyroxsulam, rimsulfuron, sulfometuron-methyl, sulfosulfuron,thiencarbazone-methyl, thifensulfuron-methyl, triasulfuron,tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl,tritosulfuron and triafamone;b3) from the group of the photosynthesis inhibitors:ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromoxyniland its salts and esters, chloridazone, chlorotoluron, cyanazine,desmedipham, diquat-dibromide, diuron, fluometuron, hexazinone, ioxyniland its salts and esters, isoproturon, lenacil, linuron, metamitron,methabenzthiazuron, metribuzin, paraquat, paraquat-dichloride,phenmedipham, propanil, pyridate, simazine, terbutryn, terbuthylazine,thidiazuron,1-(6-tert-butylpyrimidin-4-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one(CAS 1654744-66-7),1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one(CAS 1637455-12-9),1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one(CAS 1637453-94-1),1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one(CAS 1654057-29-0),1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one(CAS 1654747-80-4),4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;(CAS 2023785-78-4),4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 2023785-79-5),5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 1701416-69-4),4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one(CAS 1708087-22-2),4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one(CAS 2023785-80-8) and1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one(CAS 1844836-64-1);b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:acifluorfen-sodium, bencarbazone, benzfendizone, butafenacil,carfentrazone-ethyl, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl,flumioxazin, fluoroglycofen-ethyl, fomesafen, lactofen, oxadiargyl,oxadiazon, oxyfluorfen, pentoxazone, pyraflufen, pyraflufen-ethyl,saflufenacil, sulfentrazone, tiafenacil, trifludimoxazin, ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate(CAS 353292-31-6; S-3100),N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 452098-92-9),N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 915396-43-9),N-ethyl-3-(2-chloro-6-fluoro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide(CAS 452099-05-7),N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1HLpyrazole-1-carboxamide (CAS 452100-03-7),3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione(CAS 451484-50-7),2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione(CAS 1300118-96-0);1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione(CAS 1304113-05-0), and3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione(CAS 212754-02-4);b5) from the group of the bleacher herbicides:aclonifen, amitrole, beflubutamid, benzobicyclon, bicyclopyrone,clomazone, diflufenican, fenquinotrione, flumeturon, flurochloridone,flurtamone, isoxaflutole, mesotrione, oxotrione (CAS 1486617-21-3),norflurazon, picolinafen, pyrasulfotole, pyrazolynate, sulcotrione,tefuryltrione, tembotrione, tolpyralate, topramezone,4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine(CAS180608-33-7),2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide(CAS 1361139-71-0),2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidone (CAS81777-95-9) and2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS81778-66-7);b6) from the group of the EPSP synthase inhibitors:glyphosate, glyphosate-isopropylammonium, glyphosate-potassium andglyphosate-trimesium (sulfosate);b7) from the group of the glutamine synthase inhibitors:glufosinate, glufosinate-P, glufosinate-ammonium;b8) from the group of the DHP synthase inhibitors: asulam;b9) from the group of the mitosis inhibitors:benfluralin, dithiopyr, ethalfluralin, flamprop, flamprop-isopropyl,flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, oryzalin,pendimethalin, thiazopyr and trifluralin;b10) from the group of the VLCFA inhibitors:acetochlor, alachlor, amidochlor, anilofos, butachlor, cafenstrole,dimethenamid, dimethenamid-P, fentrazamide, flufenacet, mefenacet,metazachlor, metolachlor, S-metolachlor, naproanilide, napropamide,napropamide-M, pretilachlor, fenoxasulfone, ipfencarbazone,pyroxasulfone thenylchlor and isoxazoline-compounds of the formulaeII.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 as mentionedabove;b11) from the group of the cellulose biosynthesis inhibitors:dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and1-cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine(CAS 175899-01-1);b13) from the group of the auxinic herbicides:2,4-D and its salts and esters, aminocyclopyrachlor and its salts andesters, aminopyralid and its salts such asaminopyralid-dimethylammonium,aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, clopyralidand its salts and esters, dicamba and its salts and esters,dichlorprop-P and its salts and esters, flopyrauxifen,fluroxypyr-meptyl, halauxifen and its salts and esters (CAS943832-60-8), MCPA and its salts and esters, MCPB and its salts andesters, mecoprop-P and its salts and esters, picloram and its salts andesters, quinclorac, quinmerac, triclopyr and its salts and esters,florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9) and4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid (CAS1629965-65-6);b14) from the group of the auxin transport inhibitors: diflufenzopyr anddiflufenzopyr-sodium;b15) from the group of the other herbicides: bromobutide, cinmethylin,cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters,dalapon, difenzoquat, difenzoquat-metilsulfate, DSMA, dymron(=daimuron), indanofan, metam, methylbromide, MSMA, oxaziclomefone,pyributicarb and tridiphane.

Particularly preferred herbicides B that can be used in combination withthe forms A, B, C and/or D, preferably form C, of the formula (I)according to the present invention are:

b1) from the group of the lipid biosynthesis inhibitors:clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop-P-ethyl,pinoxaden, profoxydim, tepraloxydim, tralkoxydim,4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-72-6);4-(2′,4′-Dichloro-4-cyclopropyl[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1312337-45-3);4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one(CAS 1033757-93-5);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione(CAS 1312340-84-3);5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312337-48-6);5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one;5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1312340-82-1);5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one(CAS 1033760-55-2);4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312337-51-1);4-(2′,4′-Dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester;4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312340-83-2);4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1033760-58-5); esprocarb, prosulfocarb,thiobencarb and triallate;b2) from the group of the ALS inhibitors: bensulfuron-methyl,bispyribac-sodium, cyclosulfamuron, diclosulam, flumetsulam,flupyrsulfuron-methyl-sodium, foramsulfuron, imazamox, imazapic,imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron,iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium,mesosulfuron, metazosulfuron, nicosulfuron, penoxsulam,propoxycarbazon-sodium, propyrisulfuron, pyrazosulfuron-ethyl,pyroxsulam, rimsulfuron, sulfosulfuron, thiencarbazon-methyl,tritosulfuron and triafamone;b3) from the group of the photosynthesis inhibitors: ametryn, atrazine,diuron, fluometuron, hexazinone, isoproturon, linuron, metribuzin,paraquat, paraquat-dichloride, propanil, terbutryn, terbuthylazine,1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one(CAS 1637455-12-9),1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one(CAS 1637453-94-1),1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one(CAS 1844836-64-1);b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:flumioxazin, oxyfluorfen, pyraflufen, pyraflufen-ethyl, saflufenacil,sulfentrazone, trifludimoxazin, ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate(CAS 353292-31-6; S-3100),3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione(CAS 451484-50-7),2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione(CAS 1300118-96-0), and1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione(CAS 1304113-05-0);b5) from the group of the bleacher herbicides: amitrole, bicyclopyrone,clomazone, diflufenican, fenquinotrione, flumeturon, flurochloridone,isoxaflutole, mesotrione, oxotrione (CAS 1486617-21-3), picolinafen,sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone,2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide(CAS 1361139-71-0),2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidone (CAS81777-95-9) and2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS81778-66-7);b6) from the group of the EPSP synthase inhibitors: glyphosate,glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate);b7) from the group of the glutamine synthase inhibitors: glufosinate,glufosinate-P and glufosinate-ammonium;b9) from the group of the mitosis inhibitors: pendimethalin andtrifluralin;b10) from the group of the VLCFA inhibitors: acetochlor, cafenstrole,dimethenamid-P, fentrazamide, flufenacet, mefenacet, metazachlor,metolachlor, S-metolachlor, fenoxasulfone, ipfencarbazone andpyroxasulfone; likewise, preference is given to isoxazoline compounds ofthe formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 asmentioned above;b11) from the group of the cellulose biosynthesis inhibitors:indaziflam, isoxaben and triaziflam;b13) from the group of the auxinic herbicides: 2,4-D and its salts andesters such as clacyfos, and aminocyclopyrachlor and its salts andesters, aminopyralid and its salts and its esters, clopyralid and itssalts and esters, dicamba and its salts and esters, flopyrauxifen,fluroxypyr-meptyl, halauxifen, halauxifen-methyl, quinclorac, quinmerac,florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9) and4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid (CAS1629965-65-6;b14) from the group of the auxin transport inhibitors: diflufenzopyr anddiflufenzopyr-sodium,b15) from the group of the other herbicides: cinmethylin, dymon(=daimuron), indanofan, oxaziclomefone.

The herbicidal compounds B having a carboxyl group can be employed inform of the acid, in the form of an agriculturally suitable salt asmentioned above or else in the form of an agriculturally acceptablederivative as mentioned above.

Active compounds B and C having a carboxyl group can be employed in theform of the acid, in the form of an agriculturally suitable salt asmentioned above or else in the form of an agriculturally acceptablederivative in the compositions according to the invention.

In the case of dicamba, suitable salts include those, where thecounterion is an agriculturally acceptable cation. For example, suitablesalts of dicamba are dicamba-sodium, dicamba-potassium,dicamba-methylammonium, dicamba-dimethylammonium,dicamba-isopropylammonium, dicamba-diglycolamine, dicamba-olamine,dicamba-diolamine, dicamba-trolamine,dicamba-N,N-bis-(3-aminopropyl)methylamine anddicamba-diethylenetriamine. Examples of a suitable ester aredicamba-methyl and dicamba-butotyl.

Suitable salts of 2,4-D are 2,4-D-ammonium, 2,4-D-dimethylammonium,2,4-D-diethylammonium, 2,4-D-diethanolammonium (2,4-D-diolamine),2,4-D-triethanol-ammonium, 2,4-D-isopropylammonium,2,4-D-triisopropanolammonium, 2,4-D-heptylammonium,2,4-D-dodecylammonium, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-tris(isopropyl)-ammonium,2,4-D-trolamine, 2,4-D-lithium, 2,4-D-sodium. Examples of suitableesters of 2,4-D are 2,4-D-butotyl, 2,4-D-2-butoxypropyl,2,4-D-3-butoxypropyl, 2,4-D-butyl, 2,4-D-ethyl, 2,4-D-ethylhexyl,2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropyl, 2,4-D-meptyl,2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-propyl, 2,4-D-tefuryl andclacyfos.

Suitable salts of 2,4-DB are for example 2,4-DB-sodium, 2,4-DB-potassiumand 2,4-DB-dimethylammonium. Suitable esters of 2,4-DB are for example2,4-DB-butyl and 2,4-DB-isoctyl.

Suitable salts of dichlorprop are for example dichlorprop-sodium,dichlorprop-potassium and dichlorprop-dimethylammonium. Examples ofsuitable esters of dichlorprop are dichlorprop-butotyl anddichlorprop-isoctyl.

Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl,MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl,MCPA-2-ethylhexyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl,MCPA-isopropylammonium, MCPA-methyl, MCPA-olamine, MCPA-potassium,MCPA-sodium and MCPA-trolamine.

A suitable salt of MCPB is MCPB sodium. A suitable ester of MCPB isMCPB-ethyl. Suitable salts of clopyralid are clopyralid-potassium,clopyralid-olamine and clopyralid-tris-(2-hydroxypropyl)ammonium.Example of suitable esters of clopyralid is clopyralid-methyl.

Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl andfluroxypyr-2-butoxy-1-methylethyl, wherein fluroxypyr-meptyl ispreferred.

Suitable salts of picloram are picloram-dimethylammonium,picloram-potassium, picloram-triisopropanolammonium,picloram-triisopropylammonium and picloram-trolamine. A suitable esterof picloram is picloram-isoctyl.

A suitable salt of triclopyr is triclopyr-triethylammonium. Suitableesters of triclopyr are for example triclopyr-ethyl andtriclopyr-butotyl.

Suitable salts and esters of chloramben include chloramben-ammonium,chloramben-diolamine, chloramben-methyl, chloramben-methylammonium andchloramben-sodium. Suitable salts and esters of 2,3,6-TBA include2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium and2,3,6-TBA-sodium.

Suitable salts and esters of aminopyralid includeaminopyralid-potassium, aminopyralid-dimethylammonium, andaminopyralid-tris(2-hydroxypropyl)ammonium. Suitable salts of glyphosateare for example glyphosate-ammonium, glyphosate-diammonium,glyphosate-dimethylammonium, glyphosate-isopropylammonium,glyphosate-potassium, glyphosate-sodium, glyphosate-trimesium as well asthe ethanolamine and diethanolamine salts, preferablyglyphosate-diammonium, glyphosate-isopropylammonium andglyphosate-trimesium (sulfosate).

A suitable salt of glufosinate is for example glufosinate-ammonium.

A suitable salt of glufosinate-P is for example glufosinate-P-ammonium.Suitable salts and esters of bromoxynil are for examplebromoxynil-butyrate, bromoxynil-heptanoate, bromoxynil-octanoate,bromoxynil-potassium and bromoxynil-sodium.

Suitable salts and esters of ioxonil are for example ioxonil-octanoate,ioxonil-potassium and ioxonil-sodium.

Suitable salts and esters of mecoprop include mecoprop-butotyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop-methyl,mecoprop-potassium, mecoprop-sodium and mecoprop-trolamine.

Suitable salts of mecoprop-P are for example mecoprop-P-butotyl,mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl,mecoprop-P-isobutyl, mecoprop-P-potassium and mecoprop-P-sodium.

A suitable salt of diflufenzopyr is for example diflufenzopyr-sodium.

A suitable salt of naptalam is for example naptalam-sodium.

Suitable salts and esters of aminocyclopyrachlor are for exampleaminocyclopyrachlor-dimethylammonium, aminocyclopyrachlor-methyl,aminocyclopyrachlor-triisopropanolammonium, aminocyclopyrachlor-sodiumand aminocyclopyrachlor-potassium.

A suitable salt of quinclorac is for examplequinclorac-dimethylammonium.

A suitable salt of quinmerac is for example quinmerac-dimethylammonium.

A suitable salt of imazamox is for example imazamox-ammonium.

Suitable salts of imazapic are for example imazapic-ammonium andimazapic-isopropylammonium.

Suitable salts of imazapyr are for example imazapyr-ammonium andimazapyr-isopropylammonium.

A suitable salt of imazaquin is for example imazaquin-ammonium.

Suitable salts of imazethapyr are for example imazethapyr-ammonium andimazethapyr-isopropylammonium.

A suitable salt of topramezone is for example topramezone-sodium.

Particularly preferred herbicidal compounds Bare the herbicides Basdefined above; in particular the herbicides B.1-B.202 listed below intable B:

TABLE B Herbicide B B.1 clethodim B.2 clodinafop-propargyl B.3cycloxydim B.4 cyhalofop-butyl B.5 fenoxaprop-ethyl B.6fenoxaprop-P-ethyl B.7 metamifop B.8 pinoxaden B.9 profoxydim B.10sethoxydim B.11 tepraloxydim B.12 tralkoxydim B.13 esprocarb B.14ethofumesate B.15 molinate B.16 prosulfocarb B.17 thiobencarb B.18triallate B.19 bensulfuron-methyl B.20 bispyribac-sodium B.21cloransulam-methyl B.22 chlorsulfuron B.23 clorimuron B.24cyclosulfamuron B.25 diclosulam B.26 florasulam B.27 flumetsulam B.28flupyrsulfuron-methyl-sodium B.29 foramsulfuron B.30 imazamox B.31imazamox-ammonium B.32 imazapic B.33 imazapic-ammonium B.34imazapic-isopropylammonium B.35 imazapyr B.36 imazapyr-ammonium B.37imazapyr-isopropylammonium B.38 imazaquin B.39 imazaquin-ammonium B.40imazethapyr B.41 imazethapyr-ammonium B.42 imazethapyr-isopropylammoniumB.43 imazosulfuron B.44 iodosulfuron-methyl-sodium B.45 iofensulfuronB.46 iofensulfuron-sodium B.47 mesosulfuron-methyl B.48 metazosulfuronB.49 metsulfuron-methyl B.50 metosulam B.51 nicosulfuron B.52 penoxsulamB.53 propoxycarbazon-sodium B.54 pyrazosulfuron-ethyl B.55 pyribenzoximB.56 pyriftalid B.57 pyroxsulam B.58 propyrisulfuron B.59 rimsulfuronB.60 sulfosulfuron B.61 thiencarbazone-methyl B.62 thifensulfuron-methylB.63 tribenuron-methyl B.64 tritosulfuron B.65 triafamone B.66 ametryneB.67 atrazine B.68 bentazon B.69 bromoxynil B.70 bromoxynil-octanoateB.71 bromoxynil-heptanoate B.72 bromoxynil-potassium B.73 diuron B.74fluometuron B.75 hexazinone B.76 isoproturon B.77 linuron B.78metamitron B.79 metribuzin B.80 propanil B.81 simazin B.82terbuthylazine B.83 terbutryn B.84 paraquat-dichloride B.85 acifluorfenB.86 butafenacil B.87 carfentrazone-ethyl B.88 flumioxazin B.89fomesafen B.90 oxadiargyl B.91 oxyfluorfen B.92 pyraflufen B.93pyraflufen-ethyl B.94 saflufenacil B.95 sulfentrazone B.96trifludimoxazin B.97 ethyl [3-[2-chloro-4-fluoro- 5-(1-methyl-6-trifluoromethyl-2,4-dioxo- 1,2,3,4-tetrahydropyri-midin-3-yl)phenoxy]-2- pyridyloxy]acetate (CAS 353292-31-6) B.98benzobicyclon B.99 bicyclopyrone B.100 clomazone B.101 diflufenicanB.102 flurochloridone B.103 isoxaflutole B.104 mesotrione B.105norflurazone B.106 picolinafen B.107 sulcotrione B.108 tefuryltrioneB.109 tembotrione B.110 tolpyralate B.111 topramezone B.112topramezone-sodium B.113 amitrole B.114 fluometuron B.115 fenquinotrioneB.116 glyphosate B.117 glyphosate-ammonium B.118glyphosate-dimethylammonium B.119 glyphosate-isopropylammonium B.120glyphosate-trimesium (sulfosate) B.121 glyphosate-potassium B.122glufosinate B.123 glufosinate-ammonium B.124 glufosinate-P B.125glufosinate-P-ammonium B.126 pendimethalin B.127 trifluralin B.128acetochlor B.129 butachlor B.130 cafenstrole B.131 dimethenamid-P B.132fentrazamide B.133 flufenacet B.134 mefenacet B.135 metazachlor B.136metolachlor B.137 S-metolachlor B.138 pretilachlor B.139 fenoxasulfoneB.140 indaziflam B.141 isoxaben B.142 triaziflam B.143 ipfencarbazoneB.144 pyroxasulfone B.145 2,4-D B.146 2,4-D-isobutyl B.1472,4-D-dimethylammonium B.148 2,4-D-N,N,N-trimethylethanolammonium B.149aminopyralid B.150 aminopyralid-methyl B.151aminopyralid-dimethyl-ammonium B.152aminopyralid-tris(2-hydroxypropyl)ammonium B.153 clopyralid B.154clopyralid-methyl B.155 clopyralid-olamine B.156 dicamba B.157dicamba-butotyl B.158 dicamba-diglycolamine B.159dicamba-dimethylammonium B.160 dicamba-diolamine B.161dicamba-isopropylammonium B.162 dicamba-potassium B.163 dicamba-sodiumB.164 dicamba-trolamine B.165 dicamba-N,N-bis-(3-aminopropyl)methylamineB.166 dicamba-diethylenetriamine B.167 fluroxypyr B.168fluroxypyr-meptyl B.169 halauxifen B.170 halauxifen-methyl B.171 MCPAB.172 MCPA-2-ethylhexyl B.173 MCPA-dimethylammonium B.174 quincloracB.175 quinclorac-dimethylammonium B.176 quinmerac B.177quinmerac-dimethylammonium B.178 florpyrauxifen B.179florpyrauxifen-benzyl (CAS 1390661-72-9) B.180 aminocyclopyrachlor B.181aminocyclopyrachlor-potassium B.182 aminocyclopyrachlor-methyl B.183diflufenzopyr B.184 diflufenzopyr-sodium B.185 dymron B.186 indanofanB.187 oxaziclomefone B.188 II.1 B.189 II.2 B.190 II.3 B.191 II.4 B.192II.5 B.193 II.6 B.194 II.7 B.195 II.8 B.196 II.9 B.1974-amino-3-chloro-5-fluoro- 6-(7-fluoro-1H-indol-6- yl)picolinic acid(CAS 1629965-65-6) B.198 flopyrauxifen B.199 oxotrione (CAS1486617-21-3) B.200 cinmethylin B.201 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4- (trifluoromethyl)benzamide (CAS1361139-71-0) B.202 2-(2,4-dichlorophenyl)- methyl-4,4-dimethyl-3-isoxazolidone (CAS 81777-95-9)

Moreover, it may be useful to apply the forms A, B, C and/or D,preferably form C, of formula (I) in combination with safeners. Safenersare chemical compounds which prevent or reduce damage on useful plantswithout having a major impact on the herbicidal action of the forms A,B, C and/or D, preferably form C, towards unwanted plants. They can beapplied either before sowings (e.g. on seed treatments, shoots orseedlings) or in the pre-emergence application or post-emergenceapplication of the useful plant. The safeners and the forms A, B, Cand/or D, preferably form C, of formula (I), and optionally theherbicides B can be applied simultaneously or in succession.

In another embodiment of the present invention the compositionsaccording to the present invention comprise the forms A, B, C and/or D,preferably form C, and at least one safener C (component C).

Suitable safeners are e.g. (quinolin-8-oxy)acetic acids,1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acids,1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazol-3,5-dicarboxylic acids,4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides,alpha-oximinophenylacetonitriles, acetophenonoximes,4,6-dihalo-2-phenylpyrimidines,N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8-naphthalicanhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids,phosphorthiolates and N-alkyl-O-phenylcarbamates and theiragriculturally acceptable salts and their agriculturally acceptablederivatives such amides, esters, and thioesters, provided they have anacid group.

Suitable safeners are e.g. (quinolin-8-oxy)acetic acids,1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acids,1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazol-3,5-dicarboxylic acids,4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides,alpha-oximinophenylacetonitriles, acetophenonoximes,4,6-dihalo-2-phenylpyrimidines,N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8-naphthalicanhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids,phosphorthiolates and N-alkyl-O-phenylcarbamates and theiragriculturally acceptable salts and their agriculturally acceptablederivatives such amides, esters, and thioesters, provided they have anacid group.

Examples of preferred safeners C are benoxacor, cloquintocet,cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate,fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen,mefenpyr, mephenate, naphthalic anhydride, oxabetrinil,4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine(R-29148, CAS 52836-31-4), metcamifen (CAS 129531-12-0) and BPCMS (CAS54091-06-4).

Especially preferred safeners C are benoxacor, cloquintocet,cyprosulfamide, dichlormid, fenchlorazole, fenclorim, flurazole,fluxofenim, furilazole, isoxadifen, mefenpyr, naphthalic anhydride,oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro-[4.5]decane (MON4660,CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine(R-29148, CAS 52836-31-4) and metcamifen (CAS 129531-12-0).

Particularly preferred safeners C are benoxacor, cloquintocet,cyprosulfamide, dichlormid, fenchlorazole, fenclorim, furilazole,isoxadifen, mefenpyr, naphthalic anhydride,4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine(R-29148, CAS 52836-31-4) and metcamifen (CAS 129531-12-0).

Particularly preferred safeners C, which, as component C, areconstituent of the composition according to the invention are thesafeners C as defined above; in particular the safeners C.1-C.17 listedbelow in table C:

TABLE C Safener C C.1 benoxacor C.2 cloquintocet C.3 cloquintocet-mexylC.4 cyprosulfamide C.5 dichlormid C.6 fenchlorazole C.7fenchlorazole-ethyl C.8 fenclorim C.9 furilazole C.10 isoxadifen C.11isoxadifen-ethyl C.12 mefenpyr C.13 mefenpyr-diethyl C.14 naphtalic acidanhydride C.15 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660,CAS 71526-07-3) C.16 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine(R-29148, CAS 52836-31-4) C.17 metcamifen (CAS 129531-12-0)

The active compounds B of groups b1) to b15) and the active compounds Care known herbicides and safeners, see, for example, The Compendium ofPesticide Common Names (http://www.alanwood.net/pesticides/); FarmChemicals Handbook 2000 volume 86, Meister Publishing Company, 2000; B.Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg ThiemeVerlag, Stuttgart 1995; W. H. Ahrens, Herbicide Handbook, 7th edition,Weed Science Society of America, 1994; and K. K. Hatzios, HerbicideHandbook, Supplement for the 7th edition, Weed Science Society ofAmerica, 1998. 2,2,5-Trimethyl-3-(dichloroacetyl)-1,3-oxazolidine [CASNo. 52836-31-4] is also referred to as R-29148.4-(Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane [CAS No. 71526-07-3] isalso referred to as AD-67 and MON 4660.

The assignment of the active compounds to the respective mechanisms ofaction is based on current knowledge. If several mechanisms of actionapply to one active compound, this substance was only assigned to onemechanism of action.

According to a preferred embodiment of the invention, the compositioncomprises as herbicidal active compound B or component B at least one,preferably exactly one herbicide B.

According to another preferred embodiment of the invention, thecomposition comprises as herbicidal active compounds B or component B atleast two, preferably exactly two herbicides B different from eachother.

According to another preferred embodiment of the invention, thecomposition comprises as herbicidal active compounds B or component B atleast three, preferably exactly three herbicides B different from eachother.

According to another preferred embodiment of the invention, thecomposition comprises as safening component C or component C at leastone, preferably exactly one safener C.

According to another preferred embodiment of the invention, thecomposition comprises as component B at least one, preferably exactlyone herbicide B, and as component C at least one, preferably exactlyone, safener C.

According to another preferred embodiment of the invention, thecomposition comprises at least two, preferably exactly two, herbicides Bdifferent from each other, and as component C at least one, preferablyexactly one, safener C.

According to another preferred embodiment of the invention, thecomposition comprises at least three, preferably exactly three,herbicides B different from each other, and as component C at least one,preferably exactly one, safener C.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B or C,preferably form A or B, more preferably form A, and as component B atleast one, preferably exactly one, herbicide B.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or D,preferably form C, and at least two, preferably exactly two, herbicidesB different from each other.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or D,preferably form C, and at least three, preferably exactly three,herbicides B different from each other.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or D,preferably form C, and as component C at least one, preferably exactlyone, safener C.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or D,preferably form C, as component B at least one, preferably exactly one,herbicide B, and as component C at least one, preferably exactly onesafener C.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or D,preferably form C, as component B at least two, preferably exactly twoherbicides B different from each other, and as component C at least one,preferably exactly one, safener C.

According to another preferred embodiment of the invention, thecomposition comprises as component A at least one form A, B, C or Dpreferably form C, as component B at least three, preferably exactlythree herbicides B different from each other, and as component C atleast one, preferably exactly one, safener C.

According to another preferred embodiment of the invention, thecomposition comprises, in addition form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b1), in particular selected from the groupconsisting of clethodim, clodinafop-propargyl, cycloxydim,cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, metamifop,pinoxaden, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, esprocarb,ethofumesate, molinate, prosulfocarb, thiobencarb and triallate.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b2), in particular selected from the groupconsisting of bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl,chlorsulfuron, clorimuron, cyclosulfamuron, diclosulam, florasulam,flumetsulam, flupyrsulfuron-methyl-sodium, foramsulfuron, imazamox,imazamox-ammonium, imazapic, imazapic-ammonium,imazapic-isopropylammonium, imazapyr, imazapyr-ammonium,imazethapyr-isopropylammonium, imazaquin, imazaquin-ammonium,imazethapyr, imazethapyr-ammonium, imazethapyr-isopropylammonium,imazosulfuron, iodosulfuron-methyl-sodium, iofensulfuron,iofensulfuron-sodium, mesosulfuron-methyl, metazosulfuron,metsulfuron-methyl, metosulam, nicosulfuron, penoxsulam,propoxycarbazon-sodium, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid,pyroxsulam, propyrisulfuron, rimsulfuron, sulfosulfuron,thiencarbazon-methyl, thifensulfuron-methyl, tribenuron-methyl,tritosulfuron and triafamone.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b3), in particular selected from the groupconsisting of ametryn, atrazine, bentazon, bromoxynil,bromoxynil-octanoate, bromoxynil-heptanoate, bromoxynil-potassium,diuron, fluometuron, hexazinone, isoproturon, linuron, metamitron,metribuzin, paraquat-dichloride, propanil, simazin, terbutryn andterbuthylazine.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b4), in particular selected from the groupconsisting of acifluorfen, butafencil, carfenetrazone-ethyl,flumioxazin, fomesafen, oxadiargyl, oxyfluorfen, pyraflufen,pyraflufen-ethyl, saflufenacil, sulfentrazone, trifludimoxazin, ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate(CAS 353292-31-6; S-3100).

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b5), in particular selected from the groupconsisting of amitrole, benzobicyclon, bicyclopyrone, clomazone,diflufenican, fenquintrone, fluometuron, flurochloridone, isoxaflutole,mesotrione, norflurazone, oxotrione (CAS 1486617-21-3), picolinafen,sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone,topramezone-sodium,2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide(CAS 1361139-71-0),2-(2,4-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidone (CAS81777-95-9) and2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS81778-66-7).

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b6), in particular selected from the groupconsisting of glyphosate, glyphosate-ammonium,glyphosate-dimethylammonium, glyphosate-isopropylammonium andglyphosate-trimesium (sulfosate) and glyphosate-potassium.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b7), in particular selected from the groupconsisting of glufosinate, glufosinate-ammonium, glufosinate-P andglufosinate-P-ammonium.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b9), in particular selected from the groupconsisting of pendimethalin and trifluralin.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b10), in particular selected from the groupconsisting of acetochlor, butachlor, cafenstrole, dimethenamid-P,fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor,S-metolachlor, fenoxasulfone, ipfencarbazone and pyroxasulfone.Likewise, preference is given to compositions comprising in addition toform A, B or C, preferably form A or B, more preferably form A, at leastone and especially exactly one herbicidally active compound from groupb10), in particular selected from the group consisting of isoxazolinecompounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8and II.9, as defined above.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b11), in particular indaziflam, isoxaben andtriaziflam.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b13), in particular selected from the groupconsisting of 2,4-D, 2,4-D-isobutyl, 2,4-D-dimethylammonium,2,4-D-N,N,N-trimethylethanolammonium, aminocyclopyrachlor,aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid,aminopyralid-methyl, aminopyralid-dimethylammonium,aminopyralid-tris(2-hydroxypropyl)ammonium, clopyralid,clopyralid-methyl, clopyralid-olamine, dicamba, dicamba-butotyl,dicamba-diglycolamine, dicamba-dimethylammonium, dicamba-diolamine,dicamba-isopropylammonium, dicamba-potassium, dicamba-sodium,dicamba-trolamine, dicamba-N,N-bis-(3-aminopropyl)methylamine,dicamba-diethylenetriamine, flopyrauxifen, fluroxypyr,fluroxypyr-meptyl, halauxifen, halauxifen-methyl, MCPA,MCPA-2-ethylhexyl, MCPA-dimethylammonium, quinclorac,quinclorac-dimethylammonium, quinmerac, quinmerac-dimethylammonium,florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9), and4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid (CAS1629965-65-6).

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b14), in particular selected from the groupconsisting of diflufenzopyr, diflufenzopyr-sodium, dymron, indanofan anddiflufenzopyr-sodium.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one herbicidally activecompound from group b15), in particular selected from the groupconsisting of cinmethylin, dymron (=daimuron), indanofan andoxaziclomefone.

According to another preferred embodiment of the invention, thecomposition comprises, in addition to form A, B, C and/or D, preferablyform C, at least one and especially exactly one safener C, in particularselected from the group consisting of benoxacor, cloquintocet,cyprosulfamide, dichlormid, fenchlorazole, fenclorim, furilazole,isoxadifen, mefenpyr, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane(MON4660, CAS 71526-07-3) and2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS52836-31-4).

Here and below, the term “binary compositions” includes compositionscomprising one or more, for example 1, 2 or 3, active compounds of theformula (I) and either one or more, for example 1, 2 or 3, herbicides Bor one or more safeners C.

Correspondingly, the term “ternary compositions” includes compositionscomprising one or more, for example 1, 2 or 3, active compounds of theformula (I), one or more, for example 1, 2 or 3, herbicides B and one ormore, for example 1, 2 or 3, safeners C.

In binary compositions comprising at least one form A, B, C or D,preferably form C, as component A and at least one herbicide B, theweight ratio of the active compounds A:B is generally in the range offrom 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1,in particular in the range of from 1:250 to 250:1 and particularlypreferably in the range of from 1:75 to 75:1.

In binary compositions comprising at least form A, B, C or D, preferablyform C, as component A and at least one safener C, the weight ratio ofthe active compounds A:C is generally in the range of from 1:1000 to1000:1, preferably in the range of from 1:500 to 500:1, in particular inthe range of from 1:250 to 250:1 and particularly preferably in therange of from 1:75 to 75:1.

In ternary compositions comprising at least one form A, B, C or D,preferably form C, as component A, at least one herbicide B and at leastone safener C, the relative proportions by weight of the components A:Bare generally in the range of from 1:1000 to 1000:1, preferably in therange of from 1:500 to 500:1, in particular in the range of from 1:250to 250:1 and particularly preferably in the range of from 1:75 to 75:1,the weight ratio of the components A:C is generally in the range of from1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, inparticular in the range of from 1:250 to 250:1 and particularlypreferably in the range of from 1:75 to 75:1, and the weight ratio ofthe components B:C is generally in the range of from 1:1000 to 1000:1,preferably in the range of from 1:500 to 500:1, in particular in therange of from 1:250 to 250:1 and particularly preferably in the range offrom 1:75 to 75:1. The weight ratio of components A+B to component C ispreferably in the range of from 1:500 to 500:1, in particular in therange of from 1:250 to 250:1 and particularly preferably in the range offrom 1:75 to 75:1.

The weight ratios of the individual components in the preferred mixturesmentioned below are within the limits given herein, in particular withinthe preferred limits. Particularly preferred are the compositionsmentioned below comprising form Cas defined and the substance(s) asdefined in the respective row of table 1; especially preferredcomprising as only herbicidal active compounds form as defined and thesubstance(s) as defined in the respective row of table 1; mostpreferably comprising as only active compounds form Cas defined and thesubstance(s) as defined in the respective row of table 1.

Particularly preferred are compositions 1.1 to 1.3653, comprising thecomprising form C of the compound of formula (I) and the substance(s) asdefined in the respective row of table 1:

TABLE 1 (compositions 1.1 to 1.3653): comp. no. herbicide B safener C1.1 B.1 — 1.2 B.2 — 1.3 B.3 — 1.4 B.4 — 1.5 B.5 — 1.6 B.6 — 1.7 B.7 —1.8 B.8 — 1.9 B.9 — 1.10 B.10 — 1.11 B.11 — 1.12 B.12 — 1.13 B.13 — 1.14B.14 — 1.15 B.15 — 1.16 B.16 — 1.17 B.17 — 1.18 B.18 — 1.19 B.19 — 1.20B.20 — 1.21 B.21 — 1.22 B.22 — 1.23 B.23 — 1.24 B.24 — 1.25 B.25 — 1.26B.26 — 1.27 B.27 — 1.28 B.28 — 1.29 B.29 — 1.30 B.30 — 1.31 B.31 — 1.32B.32 — 1.33 B.33 — 1.34 B.34 — 1.35 B.35 — 1.36 B.36 — 1.37 B.37 — 1.38B.38 — 1.39 B.39 — 1.40 B.40 — 1.41 B.41 — 1.42 B.42 — 1.43 B.43 — 1.44B.44 — 1.45 B.45 — 1.46 B.46 — 1.47 B.47 — 1.48 B.48 — 1.49 B.49 — 1.50B.50 — 1.51 B.51 — 1.52 B.52 — 1.53 B.53 — 1.54 B.54 — 1.55 B.55 — 1.56B.56 — 1.57 B.57 — 1.58 B.58. — 1.59 B.59 — 1.60 B.60 — 1.61 B.61 — 1.62B.62 — 1.63 B.63 — 1.64 B.64 — 1.65 B.65 — 1.66 B.66 — 1.67 B.67 — 1.68B.68 — 1.69 B.69 — 1.70 B.70 — 1.71 B.71 — 1.72 B.72 — 1.73 B.73 — 1.74B.74 — 1.75 B.75 — 1.76 B.76 — 1.77 B.77 — 1.78 B.78 — 1.79 B.79 — 1.80B.80 — 1.81 B.81 — 1.82 B.82 — 1.83 B.83 — 1.84 B.84 — 1.85 B.85 — 1.86B.86 — 1.87 B.87 — 1.88 B.88 — 1.89 B.89 — 1.90 B.90 — 1.91 B.91 — 1.92B.92 — 1.93 B.93 — 1.94 B.94 — 1.95 B.95 — 1.96 B.96 — 1.97 B.97 — 1.98B.98 — 1.99 B.99 — 1.100 B.100 — 1.101 B.101 — 1.102 B.102 — 1.103 B.103— 1.104 B.104 — 1.105 B.105 — 1.106 B.106 — 1.107 B.107 — 1.108 B.108 —1.109 B.109 — 1.110 B.110 — 1.111 B.111 — 1.112 B.112 — 1.113 B.113 —1.114 B.114 — 1.115 B.115 — 1.116 B.116 — 1.117 B.117 — 1.118 B.118 —1.119 B.119 — 1.120 B.120 — 1.121 B.121 — 1.122 B.122 — 1.123 B.123 —1.124 B.124 — 1.125 B.125 — 1.126 B.126 — 1.127 B.127 — 1.128 B.128 —1.129 B.129 — 1.130 B.130 — 1.131 B.131 — 1.132 B.132 — 1.133 B.133 —1.134 B.134 — 1.135 B.135 — 1.136 B.136 — 1.137 B.137 — 1.138 B.138 —1.139 B.139 — 1.140 B.140 — 1.141 B.141 — 1.142 B.142 — 1.143 B.143 —1.144 B.144 — 1.145 B.145 — 1.146 B.146 — 1.147 B.147 — 1.148 B.148 —1.149 B.149 — 1.150 B.150 — 1.151 B.151 — 1.152 B.152 — 1.153 B.153 —1.154 B.154 — 1.155 B.155 — 1.156 B.156 — 1.157 B.157 — 1.158 B.158 —1.159 B.159 — 1.160 B.160 — 1.161 B.161 — 1.162 B.162 — 1.163 B.163 —1.164 B.164 — 1.165 B.165 — 1.166 B.166 — 1.167 B.167 — 1.168 B.168 —1.169 B.169 — 1.170 B.170 — 1.171 B.171 — 1.172 B.172 — 1.173 B.173 —1.174 B.174 — 1.175 B.175 — 1.176 B.176 — 1.177 B.177 — 1.178 B.178 —1.179 B.179 — 1.180 B.180 — 1.181 B.181 — 1.182 B.182 — 1.183 B.183 —1.184 B.184 — 1.185 B.185 — 1.186 B.186 — 1.187 B.187 — 1.188 B.188 —1.189 B.189 — 1.190 B.190 — 1.191 B.191 — 1.192 B.192 — 1.193 B.193 —1.194 B.194 — 1.195 B.195 — 1.196 B.196 — 1.197 B.197 — 1.198 B.198 —1.199 B.199 — 1.200 B.200 — 1.201 B.201 — 1.202 B.202 — 1.203 B.1 C.11.204 B.2 C.1 1.205 B.3 C.1 1.206 B.4 C.1 1.207 B.5 C.1 1.208 B.6 C.11.209 B.7 C.1 1.210 B.8 C.1 1.211 B.9 C.1 1.212 B.10 C.1 1.213 B.11 C.11.214 B.12 C.1 1.215 B.13 C.1 1.216 B.14 C.1 1.217 B.15 C.1 1.218 B.16C.1 1.219 B.17 C.1 1.220 B.18 C.1 1.221 B.19 C.1 1.222 B.20 C.1 1.223B.21 C.1 1.224 B.22 C.1 1.225 B.23 C.1 1.226 B.24 C.1 1.227 B.25 C.11.228 B.26 C.1 1.229 B.27 C.1 1.230 B.28 C.1 1.231 B.29 C.1 1.232 B.30C.1 1.233 B.31 C.1 1.234 B.32 C.1 1.235 B.33 C.1 1.236 B.34 C.1 1.237B.35 C.1 1.238 B.36 C.1 1.239 B.37 C.1 1.240 B.38 C.1 1.241 B.39 C.11.242 B.40 C.1 1.243 B.41 C.1 1.244 B.42 C.1 1.245 B.43 C.1 1.246 B.44C.1 1.247 B.45 C.1 1.248 B.46 C.1 1.249 B.47 C.1 1.250 B.48 C.1 1.251B.49 C.1 1.252 B.50 C.1 1.253 B.51 C.1 1.254 B.52 C.1 1.255 B.53 C.11.256 B.54 C.1 1.257 B.55 C.1 1.258 B.56 C.1 1.259 B.57 C.1 1.260 B.58.C.1 1.261 B.59 C.1 1.262 B.60 C.1 1.263 B.61 C.1 1.264 B.62 C.1 1.265B.63 C.1 1.266 B.64 C.1 1.267 B.65 C.1 1.268 B.66 C.1 1.269 B.67 C.11.270 B.68 C.1 1.271 B.69 C.1 1.272 B.70 C.1 1.273 B.71 C.1 1.274 B.72C.1 1.275 B.73 C.1 1.276 B.74 C.1 1.277 B.75 C.1 1.278 B.76 C.1 1.279B.77 C.1 1.280 B.78 C.1 1.281 B.79 C.1 1.282 B.80 C.1 1.283 B.81 C.11.284 B.82 C.1 1.285 B.83 C.1 1.286 B.84 C.1 1.287 B.85 C.1 1.288 B.86C.1 1.289 B.87 C.1 1.290 B.88 C.1 1.291 B.89 C.1 1.292 B.90 C.1 1.293B.91 C.1 1.294 B.92 C.1 1.295 B.93 C.1 1.296 B.94 C.1 1.297 B.95 C.11.298 B.96 C.1 1.299 B.97 C.1 1.300 B.98 C.1 1.301 B.99 C.1 1.302 B.100C.1 1.303 B.101 C.1 1.304 B.102 C.1 1.305 B.103 C.1 1.306 B.104 C.11.307 B.105 C.1 1.308 B.106 C.1 1.309 B.107 C.1 1.310 B.108 C.1 1.311B.109 C.1 1.312 B.110 C.1 1.313 B.111 C.1 1.314 B.112 C.1 1.315 B.113C.1 1.316 B.114 C.1 1.317 B.115 C.1 1.318 B.116 C.1 1.319 B.117 C.11.320 B.118 C.1 1.321 B.119 C.1 1.322 B.120 C.1 1.323 B.121 C.1 1.324B.122 C.1 1.325 B.123 C.1 1.326 B.124 C.1 1.327 B.125 C.1 1.328 B.126C.1 1.329 B.127 C.1 1.330 B.128 C.1 1.331 B.129 C.1 1.332 B.130 C.11.333 B.131 C.1 1.334 B.132 C.1 1.335 B.133 C.1 1.336 B.134 C.1 1.337B.135 C.1 1.338 B.136 C.1 1.339 B.137 C.1 1.340 B.138 C.1 1.341 B.139C.1 1.342 B.140 C.1 1.343 B.141 C.1 1.344 B.142 C.1 1.345 B.143 C.11.346 B.144 C.1 1.347 B.145 C.1 1.348 B.146 C.1 1.349 B.147 C.1 1.350B.148 C.1 1.351 B.149 C.1 1.352 B.150 C.1 1.353 B.151 C.1 1.354 B.152C.1 1.355 B.153 C.1 1.356 B.154 C.1 1.357 B.155 C.1 1.358 B.156 C.11.359 B.157 C.1 1.360 B.158 C.1 1.361 B.159 C.1 1.362 B.160 C.1 1.363B.161 C.1 1.364 B.162 C.1 1.365 B.163 C.1 1.366 B.164 C.1 1.367 B.165C.1 1.368 B.166 C.1 1.369 B.167 C.1 1.370 B.168 C.1 1.371 B.169 C.11.372 B.170 C.1 1.373 B.171 C.1 1.374 B.172 C.1 1.375 B.173 C.1 1.376B.174 C.1 1.377 B.175 C.1 1.378 B.176 C.1 1.379 B.177 C.1 1.380 B.178C.1 1.381 B.179 C.1 1.382 B.180 C.1 1.383 B.181 C.1 1.384 B.182 C.11.385 B.183 C.1 1.386 B.184 C.1 1.387 B.185 C.1 1.388 B.186 C.1 1.389B.187 C.1 1.390 B.188 C.1 1.391 B.189 C.1 1.392 B.190 C.1 1.393 B.191C.1 1.394 B.192 C.1 1.395 B.193 C.1 1.396 B.194 C.1 1.397 B.195 C.11.398 B.196 C.1 1.399 B.197 C.1 1.400 B.198 C.1 1.401 B.199 C.1 1.402B.200 C.1 1.403 B.201 C.1 1.404 B.202 C.1 1.405 B.1 C.2 1.406 B.2 C.21.407 B.3 C.2 1.408 B.4 C.2 1.409 B.5 C.2 1.410 B.6 C.2 1.411 B.7 C.21.412 B.8 C.2 1.413 B.9 C.2 1.414 B.10 C.2 1.415 B.11 C.2 1.416 B.12 C.21.417 B.13 C.2 1.418 B.14 C.2 1.419 B.15 C.2 1.420 B.16 C.2 1.421 B.17C.2 1.422 B.18 C.2 1.423 B.19 C.2 1.424 B.20 C.2 1.425 B.21 C.2 1.426B.22 C.2 1.427 B.23 C.2 1.428 B.24 C.2 1.429 B.25 C.2 1.430 B.26 C.21.431 B.27 C.2 1.432 B.28 C.2 1.433 B.29 C.2 1.434 B.30 C.2 1.435 B.31C.2 1.436 B.32 C.2 1.437 B.33 C.2 1.438 B.34 C.2 1.439 B.35 C.2 1.440B.36 C.2 1.441 B.37 C.2 1.442 B.38 C.2 1.443 B.39 C.2 1.444 B.40 C.21.445 B.41 C.2 1.446 B.42 C.2 1.447 B.43 C.2 1.448 B.44 C.2 1.449 B.45C.2 1.450 B.46 C.2 1.451 B.47 C.2 1.452 B.48 C.2 1.453 B.49 C.2 1.454B.50 C.2 1.455 B.51 C.2 1.456 B.52 C.2 1.457 B.53 C.2 1.458 B.54 C.21.459 B.55 C.2 1.460 B.56 C.2 1.461 B.57 C.2 1.462 B.58. C.2 1.463 B.59C.2 1.464 B.60 C.2 1.465 B.61 C.2 1.466 B.62 C.2 1.467 B.63 C.2 1.468B.64 C.2 1.469 B.65 C.2 1.470 B.66 C.2 1.471 B.67 C.2 1.472 B.68 C.21.473 B.69 C.2 1.474 B.70 C.2 1.475 B.71 C.2 1.476 B.72 C.2 1.477 B.73C.2 1.478 B.74 C.2 1.479 B.75 C.2 1.480 B.76 C.2 1.481 B.77 C.2 1.482B.78 C.2 1.483 B.79 C.2 1.484 B.80 C.2 1.485 B.81 C.2 1.486 B.82 C.21.487 B.83 C.2 1.488 B.84 C.2 1.489 B.85 C.2 1.490 B.86 C.2 1.491 B.87C.2 1.492 B.88 C.2 1.493 B.89 C.2 1.494 B.90 C.2 1.495 B.91 C.2 1.496B.92 C.2 1.497 B.93 C.2 1.498 B.94 C.2 1.499 B.95 C.2 1.500 B.96 C.21.501 B.97 C.2 1.502 B.98 C.2 1.503 B.99 C.2 1.504 B.100 C.2 1.505 B.101C.2 1.506 B.102 C.2 1.507 B.103 C.2 1.508 B.104 C.2 1.509 B.105 C.21.510 B.106 C.2 1.511 B.107 C.2 1.512 B.108 C.2 1.513 B.109 C.2 1.514B.110 C.2 1.515 B.111 C.2 1.516 B.112 C.2 1.517 B.113 C.2 1.518 B.114C.2 1.519 B.115 C.2 1.520 B.116 C.2 1.521 B.117 C.2 1.522 B.118 C.21.523 B.119 C.2 1.524 B.120 C.2 1.525 B.121 C.2 1.526 B.122 C.2 1.527B.123 C.2 1.528 B.124 C.2 1.529 B.125 C.2 1.530 B.126 C.2 1.531 B.127C.2 1.532 B.128 C.2 1.533 B.129 C.2 1.534 B.130 C.2 1.535 B.131 C.21.536 B.132 C.2 1.537 B.133 C.2 1.538 B.134 C.2 1.539 B.135 C.2 1.540B.136 C.2 1.541 B.137 C.2 1.542 B.138 C.2 1.543 B.139 C.2 1.544 B.140C.2 1.545 B.141 C.2 1.546 B.142 C.2 1.547 B.143 C.2 1.548 B.144 C.21.549 B.145 C.2 1.550 B.146 C.2 1.551 B.147 C.2 1.552 B.148 C.2 1.553B.149 C.2 1.554 B.150 C.2 1.555 B.151 C.2 1.556 B.152 C.2 1.557 B.153C.2 1.558 B.154 C.2 1.559 B.155 C.2 1.560 B.156 C.2 1.561 B.157 C.21.562 B.158 C.2 1.563 B.159 C.2 1.564 B.160 C.2 1.565 B.161 C.2 1.566B.162 C.2 1.567 B.163 C.2 1.568 B.164 C.2 1.569 B.165 C.2 1.570 B.166C.2 1.571 B.167 C.2 1.572 B.168 C.2 1.573 B.169 C.2 1.574 B.170 C.21.575 B.171 C.2 1.576 B.172 C.2 1.577 B.173 C.2 1.578 B.174 C.2 1.579B.175 C.2 1.580 B.176 C.2 1.581 B.177 C.2 1.582 B.178 C.2 1.583 B.179C.2 1.584 B.180 C.2 1.585 B.181 C.2 1.586 B.182 C.2 1.587 B.183 C.21.588 B.184 C.2 1.589 B.185 C.2 1.590 B.186 C.2 1.591 B.187 C.2 1.592B.188 C.2 1.593 B.189 C.2 1.594 B.190 C.2 1.595 B.191 C.2 1.596 B.192C.2 1.597 B.193 C.2 1.598 B.194 C.2 1.599 B.195 C.2 1.600 B.196 C.21.601 B.197 C.2 1.602 B.198 C.2 1.603 B.199 C.2 1.604 B.200 C.2 1.605B.201 C.2 1.606 B.202 C.2 1.607 B.1 C.3 1.608 B.2 C.3 1.609 B.3 C.31.610 B.4 C.3 1.611 B.5 C.3 1.612 B.6 C.3 1.613 B.7 C.3 1.614 B.8 C.31.615 B.9 C.3 1.616 B.10 C.3 1.617 B.11 C.3 1.618 B.12 C.3 1.619 B.13C.3 1.620 B.14 C.3 1.621 B.15 C.3 1.622 B.16 C.3 1.623 B.17 C.3 1.624B.18 C.3 1.625 B.19 C.3 1.626 B.20 C.3 1.627 B.21 C.3 1.628 B.22 C.31.629 B.23 C.3 1.630 B.24 C.3 1.631 B.25 C.3 1.632 B.26 C.3 1.633 B.27C.3 1.634 B.28 C.3 1.635 B.29 C.3 1.636 B.30 C.3 1.637 B.31 C.3 1.638B.32 C.3 1.639 B.33 C.3 1.640 B.34 C.3 1.641 B.35 C.3 1.642 B.36 C.31.643 B.37 C.3 1.644 B.38 C.3 1.645 B.39 C.3 1.646 B.40 C.3 1.647 B.41C.3 1.648 B.42 C.3 1.649 B.43 C.3 1.650 B.44 C.3 1.651 B.45 C.3 1.652B.46 C.3 1.653 B.47 C.3 1.654 B.48 C.3 1.655 B.49 C.3 1.656 B.50 C.31.657 B.51 C.3 1.658 B.52 C.3 1.659 B.53 C.3 1.660 B.54 C.3 1.661 B.55C.3 1.662 B.56 C.3 1.663 B.57 C.3 1.664 B.58. C.3 1.665 B.59 C.3 1.666B.60 C.3 1.667 B.61 C.3 1.668 B.62 C.3 1.669 B.63 C.3 1.670 B.64 C.31.671 B.65 C.3 1.672 B.66 C.3 1.673 B.67 C.3 1.674 B.68 C.3 1.675 B.69C.3 1.676 B.70 C.3 1.677 B.71 C.3 1.678 B.72 C.3 1.679 B.73 C.3 1.680B.74 C.3 1.681 B.75 C.3 1.682 B.76 C.3 1.683 B.77 C.3 1.684 B.78 C.31.685 B.79 C.3 1.686 B.80 C.3 1.687 B.81 C.3 1.688 B.82 C.3 1.689 B.83C.3 1.690 B.84 C.3 1.691 B.85 C.3 1.692 B.86 C.3 1.693 B.87 C.3 1.694B.88 C.3 1.695 B.89 C.3 1.696 B.90 C.3 1.697 B.91 C.3 1.698 B.92 C.31.699 B.93 C.3 1.700 B.94 C.3 1.701 B.95 C.3 1.702 B.96 C.3 1.703 B.97C.3 1.704 B.98 C.3 1.705 B.99 C.3 1.706 B.100 C.3 1.707 B.101 C.3 1.708B.102 C.3 1.709 B.103 C.3 1.710 B.104 C.3 1.711 B.105 C.3 1.712 B.106C.3 1.713 B.107 C.3 1.714 B.108 C.3 1.715 B.109 C.3 1.716 B.110 C.31.717 B.111 C.3 1.718 B.112 C.3 1.719 B.113 C.3 1.720 B.114 C.3 1.721B.115 C.3 1.722 B.116 C.3 1.723 B.117 C.3 1.724 B.118 C.3 1.725 B.119C.3 1.726 B.120 C.3 1.727 B.121 C.3 1.728 B.122 C.3 1.729 B.123 C.31.730 B.124 C.3 1.731 B.125 C.3 1.732 B.126 C.3 1.733 B.127 C.3 1.734B.128 C.3 1.735 B.129 C.3 1.736 B.130 C.3 1.737 B.131 C.3 1.738 B.132C.3 1.739 B.133 C.3 1.740 B.134 C.3 1.741 B.135 C.3 1.742 B.136 C.31.743 B.137 C.3 1.744 B.138 C.3 1.745 B.139 C.3 1.746 B.140 C.3 1.747B.141 C.3 1.748 B.142 C.3 1.749 B.143 C.3 1.750 B.144 C.3 1.751 B.145C.3 1.752 B.146 C.3 1.753 B.147 C.3 1.754 B.148 C.3 1.755 B.149 C.31.756 B.150 C.3 1.757 B.151 C.3 1.758 B.152 C.3 1.759 B.153 C.3 1.760B.154 C.3 1.761 B.155 C.3 1.762 B.156 C.3 1.763 B.157 C.3 1.764 B.158C.3 1.765 B.159 C.3 1.766 B.160 C.3 1.767 B.161 C.3 1.768 B.162 C.31.769 B.163 C.3 1.770 B.164 C.3 1.771 B.165 C.3 1.772 B.166 C.3 1.773B.167 C.3 1.774 B.168 C.3 1.775 B.169 C.3 1.776 B.170 C.3 1.777 B.171C.3 1.778 B.172 C.3 1.779 B.173 C.3 1.780 B.174 C.3 1.781 B.175 C.31.782 B.176 C.3 1.783 B.177 C.3 1.784 B.178 C.3 1.785 B.179 C.3 1.786B.180 C.3 1.787 B.181 C.3 1.788 B.182 C.3 1.789 B.183 C.3 1.790 B.184C.3 1.791 B.185 C.3 1.792 B.186 C.3 1.793 B.187 C.3 1.794 B.188 C.31.795 B.189 C.3 1.796 B.190 C.3 1.797 B.191 C.3 1.798 B.192 C.3 1.799B.193 C.3 1.800 B.194 C.3 1.801 B.195 C.3 1.802 B.196 C.3 1.803 B.197C.3 1.804 B.198 C.3 1.805 B.199 C.3 1.806 B.200 C.3 1.807 B.201 C.31.808 B.202 C.3 1.809 B.1 C.4 1.810 B.2 C.4 1.811 B.3 C.4 1.812 B.4 C.41.813 B.5 C.4 1.814 B.6 C.4 1.815 B.7 C.4 1.816 B.8 C.4 1.817 B.9 C.41.818 B.10 C.4 1.819 B.11 C.4 1.820 B.12 C.4 1.821 B.13 C.4 1.822 B.14C.4 1.823 B.15 C.4 1.824 B.16 C.4 1.825 B.17 C.4 1.826 B.18 C.4 1.827B.19 C.4 1.828 B.20 C.4 1.829 B.21 C.4 1.830 B.22 C.4 1.831 B.23 C.41.832 B.24 C.4 1.833 B.25 C.4 1.834 B.26 C.4 1.835 B.27 C.4 1.836 B.28C.4 1.837 B.29 C.4 1.838 B.30 C.4 1.839 B.31 C.4 1.840 B.32 C.4 1.841B.33 C.4 1.842 B.34 C.4 1.843 B.35 C.4 1.844 B.36 C.4 1.845 B.37 C.41.846 B.38 C.4 1.847 B.39 C.4 1.848 B.40 C.4 1.849 B.41 C.4 1.850 B.42C.4 1.851 B.43 C.4 1.852 B.44 C.4 1.853 B.45 C.4 1.854 B.46 C.4 1.855B.47 C.4 1.856 B.48 C.4 1.857 B.49 C.4 1.858 B.50 C.4 1.859 B.51 C.41.860 B.52 C.4 1.861 B.53 C.4 1.862 B.54 C.4 1.863 B.55 C.4 1.864 B.56C.4 1.865 B.57 C.4 1.866 B.58. C.4 1.867 B.59 C.4 1.868 B.60 C.4 1.869B.61 C.4 1.870 B.62 C.4 1.871 B.63 C.4 1.872 B.64 C.4 1.873 B.65 C.41.874 B.66 C.4 1.875 B.67 C.4 1.876 B.68 C.4 1.877 B.69 C.4 1.878 B.70C.4 1.879 B.71 C.4 1.880 B.72 C.4 1.881 B.73 C.4 1.882 B.74 C.4 1.883B.75 C.4 1.884 B.76 C.4 1.885 B.77 C.4 1.886 B.78 C.4 1.887 B.79 C.41.888 B.80 C.4 1.889 B.81 C.4 1.890 B.82 C.4 1.891 B.83 C.4 1.892 B.84C.4 1.893 B.85 C.4 1.894 B.86 C.4 1.895 B.87 C.4 1.896 B.88 C.4 1.897B.89 C.4 1.898 B.90 C.4 1.899 B.91 C.4 1.900 B.92 C.4 1.901 B.93 C.41.902 B.94 C.4 1.903 B.95 C.4 1.904 B.96 C.4 1.905 B.97 C.4 1.906 B.98C.4 1.907 B.99 C.4 1.908 B.100 C.4 1.909 B.101 C.4 1.910 B.102 C.4 1.911B.103 C.4 1.912 B.104 C.4 1.913 B.105 C.4 1.914 B.106 C.4 1.915 B.107C.4 1.916 B.108 C.4 1.917 B.109 C.4 1.918 B.110 C.4 1.919 B.111 C.41.920 B.112 C.4 1.921 B.113 C.4 1.922 B.114 C.4 1.923 B.115 C.4 1.924B.116 C.4 1.925 B.117 C.4 1.926 B.118 C.4 1.927 B.119 C.4 1.928 B.120C.4 1.929 B.121 C.4 1.930 B.122 C.4 1.931 B.123 C.4 1.932 B.124 C.41.933 B.125 C.4 1.934 B.126 C.4 1.935 B.127 C.4 1.936 B.128 C.4 1.937B.129 C.4 1.938 B.130 C.4 1.939 B.131 C.4 1.940 B.132 C.4 1.941 B.133C.4 1.942 B.134 C.4 1.943 B.135 C.4 1.944 B.136 C.4 1.945 B.137 C.41.946 B.138 C.4 1.947 B.139 C.4 1.948 B.140 C.4 1.949 B.141 C.4 1.950B.142 C.4 1.951 B.143 C.4 1.952 B.144 C.4 1.953 B.145 C.4 1.954 B.146C.4 1.955 B.147 C.4 1.956 B.148 C.4 1.957 B.149 C.4 1.958 B.150 C.41.959 B.151 C.4 1.960 B.152 C.4 1.961 B.153 C.4 1.962 B.154 C.4 1.963B.155 C.4 1.964 B.156 C.4 1.965 B.157 C.4 1.966 B.158 C.4 1.967 B.159C.4 1.968 B.160 C.4 1.969 B.161 C.4 1.970 B.162 C.4 1.971 B.163 C.41.972 B.164 C.4 1.973 B.165 C.4 1.974 B.166 C.4 1.975 B.167 C.4 1.976B.168 C.4 1.977 B.169 C.4 1.978 B.170 C.4 1.979 B.171 C.4 1.980 B.172C.4 1.981 B.173 C.4 1.982 B.174 C.4 1.983 B.175 C.4 1.984 B.176 C.41.985 B.177 C.4 1.986 B.178 C.4 1.987 B.179 C.4 1.988 B.180 C.4 1.989B.181 C.4 1.990 B.182 C.4 1.991 B.183 C.4 1.992 B.184 C.4 1.993 B.185C.4 1.994 B.186 C.4 1.995 B.187 C.4 1.996 B.188 C.4 1.997 B.189 C.41.998 B.190 C.4 1.999 B.191 C.4 1.1000 B.192 C.4 1.1001 B.193 C.4 1.1002B.194 C.4 1.1003 B.195 C.4 1.1004 B.196 C.4 1.1005 B.197 C.4 1.1006B.198 C.4 1.1007 B.199 C.4 1.1008 B.200 C.4 1.1009 B.201 C.4 1.1010B.202 C.4 1.1011 B.1 C.5 1.1012 B.2 C.5 1.1013 B.3 C.5 1.1014 B.4 C.51.1015 B.5 C.5 1.1016 B.6 C.5 1.1017 B.7 C.5 1.1018 B.8 C.5 1.1019 B.9C.5 1.1020 B.10 C.5 1.1021 B.11 C.5 1.1022 B.12 C.5 1.1023 B.13 C.51.1024 B.14 C.5 1.1025 B.15 C.5 1.1026 B.16 C.5 1.1027 B.17 C.5 1.1028B.18 C.5 1.1029 B.19 C.5 1.1030 B.20 C.5 1.1031 B.21 C.5 1.1032 B.22 C.51.1033 B.23 C.5 1.1034 B.24 C.5 1.1035 B.25 C.5 1.1036 B.26 C.5 1.1037B.27 C.5 1.1038 B.28 C.5 1.1039 B.29 C.5 1.1040 B.30 C.5 1.1041 B.31 C.51.1042 B.32 C.5 1.1043 B.33 C.5 1.1044 B.34 C.5 1.1045 B.35 C.5 1.1046B.36 C.5 1.1047 B.37 C.5 1.1048 B.38 C.5 1.1049 B.39 C.5 1.1050 B.40 C.51.1051 B.41 C.5 1.1052 B.42 C.5 1.1053 B.43 C.5 1.1054 B.44 C.5 1.1055B.45 C.5 1.1056 B.46 C.5 1.1057 B.47 C.5 1.1058 B.48 C.5 1.1059 B.49 C.51.1060 B.50 C.5 1.1061 B.51 C.5 1.1062 B.52 C.5 1.1063 B.53 C.5 1.1064B.54 C.5 1.1065 B.55 C.5 1.1066 B.56 C.5 1.1067 B.57 C.5 1.1068 B.58.C.5 1.1069 B.59 C.5 1.1070 B.60 C.5 1.1071 B.61 C.5 1.1072 B.62 C.51.1073 B.63 C.5 1.1074 B.64 C.5 1.1075 B.65 C.5 1.1076 B.66 C.5 1.1077B.67 C.5 1.1078 B.68 C.5 1.1079 B.69 C.5 1.1080 B.70 C.5 1.1081 B.71 C.51.1082 B.72 C.5 1.1083 B.73 C.5 1.1084 B.74 C.5 1.1085 B.75 C.5 1.1086B.76 C.5 1.1087 B.77 C.5 1.1088 B.78 C.5 1.1089 B.79 C.5 1.1090 B.80 C.51.1091 B.81 C.5 1.1092 B.82 C.5 1.1093 B.83 C.5 1.1094 B.84 C.5 1.1095B.85 C.5 1.1096 B.86 C.5 1.1097 B.87 C.5 1.1098 B.88 C.5 1.1099 B.89 C.51.1100 B.90 C.5 1.1101 B.91 C.5 1.1102 B.92 C.5 1.1103 B.93 C.5 1.1104B.94 C.5 1.1105 B.95 C.5 1.1106 B.96 C.5 1.1107 B.97 C.5 1.1108 B.98 C.51.1109 B.99 C.5 1.1110 B.100 C.5 1.1111 B.101 C.5 1.1112 B.102 C.51.1113 B.103 C.5 1.1114 B.104 C.5 1.1115 B.105 C.5 1.1116 B.106 C.51.1117 B.107 C.5 1.1118 B.108 C.5 1.1119 B.109 C.5 1.1120 B.110 C.51.1121 B.111 C.5 1.1122 B.112 C.5 1.1123 B.113 C.5 1.1124 B.114 C.51.1125 B.115 C.5 1.1126 B.116 C.5 1.1127 B.117 C.5 1.1128 B.118 C.51.1129 B.119 C.5 1.1130 B.120 C.5 1.1131 B.121 C.5 1.1132 B.122 C.51.1133 B.123 C.5 1.1134 B.124 C.5 1.1135 B.125 C.5 1.1136 B.126 C.51.1137 B.127 C.5 1.1138 B.128 C.5 1.1139 B.129 C.5 1.1140 B.130 C.51.1141 B.131 C.5 1.1142 B.132 C.5 1.1143 B.133 C.5 1.1144 B.134 C.51.1145 B.135 C.5 1.1146 B.136 C.5 1.1147 B.137 C.5 1.1148 B.138 C.51.1149 B.139 C.5 1.1150 B.140 C.5 1.1151 B.141 C.5 1.1152 B.142 C.51.1153 B.143 C.5 1.1154 B.144 C.5 1.1155 B.145 C.5 1.1156 B.146 C.51.1157 B.147 C.5 1.1158 B.148 C.5 1.1159 B.149 C.5 1.1160 B.150 C.51.1161 B.151 C.5 1.1162 B.152 C.5 1.1163 B.153 C.5 1.1164 B.154 C.51.1165 B.155 C.5 1.1166 B.156 C.5 1.1167 B.157 C.5 1.1168 B.158 C.51.1169 B.159 C.5 1.1170 B.160 C.5 1.1171 B.161 C.5 1.1172 B.162 C.51.1173 B.163 C.5 1.1174 B.164 C.5 1.1175 B.165 C.5 1.1176 B.166 C.51.1177 B.167 C.5 1.1178 B.168 C.5 1.1179 B.169 C.5 1.1180 B.170 C.51.1181 B.171 C.5 1.1182 B.172 C.5 1.1183 B.173 C.5 1.1184 B.174 C.51.1185 B.175 C.5 1.1186 B.176 C.5 1.1187 B.177 C.5 1.1188 B.178 C.51.1189 B.179 C.5 1.1190 B.180 C.5 1.1191 B.181 C.5 1.1192 B.182 C.51.1193 B.183 C.5 1.1194 B.184 C.5 1.1195 B.185 C.5 1.1196 B.186 C.51.1197 B.187 C.5 1.1198 B.188 C.5 1.1199 B.189 C.5 1.1200 B.190 C.51.1201 B.191 C.5 1.1202 B.192 C.5 1.1203 B.193 C.5 1.1204 B.194 C.51.1205 B.195 C.5 1.1206 B.196 C.5 1.1207 B.197 C.5 1.1208 B.198 C.51.1209 B.199 C.5 1.1210 B.200 C.5 1.1211 B.201 C.5 1.1212 B.202 C.51.1213 B.1 C.6 1.1214 B.2 C.6 1.1215 B.3 C.6 1.1216 B.4 C.6 1.1217 B.5C.6 1.1218 B.6 C.6 1.1219 B.7 C.6 1.1220 B.8 C.6 1.1221 B.9 C.6 1.1222B.10 C.6 1.1223 B.11 C.6 1.1224 B.12 C.6 1.1225 B.13 C.6 1.1226 B.14 C.61.1227 B.15 C.6 1.1228 B.16 C.6 1.1229 B.17 C.6 1.1230 B.18 C.6 1.1231B.19 C.6 1.1232 B.20 C.6 1.1233 B.21 C.6 1.1234 B.22 C.6 1.1235 B.23 C.61.1236 B.24 C.6 1.1237 B.25 C.6 1.1238 B.26 C.6 1.1239 B.27 C.6 1.1240B.28 C.6 1.1241 B.29 C.6 1.1242 B.30 C.6 1.1243 B.31 C.6 1.1244 B.32 C.61.1245 B.33 C.6 1.1246 B.34 C.6 1.1247 B.35 C.6 1.1248 B.36 C.6 1.1249B.37 C.6 1.1250 B.38 C.6 1.1251 B.39 C.6 1.1252 B.40 C.6 1.1253 B.41 C.61.1254 B.42 C.6 1.1255 B.43 C.6 1.1256 B.44 C.6 1.1257 B.45 C.6 1.1258B.46 C.6 1.1259 B.47 C.6 1.1260 B.48 C.6 1.1261 B.49 C.6 1.1262 B.50 C.61.1263 B.51 C.6 1.1264 B.52 C.6 1.1265 B.53 C.6 1.1266 B.54 C.6 1.1267B.55 C.6 1.1268 B.56 C.6 1.1269 B.57 C.6 1.1270 B.58. C.6 1.1271 B.59C.6 1.1272 B.60 C.6 1.1273 B.61 C.6 1.1274 B.62 C.6 1.1275 B.63 C.61.1276 B.64 C.6 1.1277 B.65 C.6 1.1278 B.66 C.6 1.1279 B.67 C.6 1.1280B.68 C.6 1.1281 B.69 C.6 1.1282 B.70 C.6 1.1283 B.71 C.6 1.1284 B.72 C.61.1285 B.73 C.6 1.1286 B.74 C.6 1.1287 B.75 C.6 1.1288 B.76 C.6 1.1289B.77 C.6 1.1290 B.78 C.6 1.1291 B.79 C.6 1.1292 B.80 C.6 1.1293 B.81 C.61.1294 B.82 C.6 1.1295 B.83 C.6 1.1296 B.84 C.6 1.1297 B.85 C.6 1.1298B.86 C.6 1.1299 B.87 C.6 1.1300 B.88 C.6 1.1301 B.89 C.6 1.1302 B.90 C.61.1303 B.91 C.6 1.1304 B.92 C.6 1.1305 B.93 C.6 1.1306 B.94 C.6 1.1307B.95 C.6 1.1308 B.96 C.6 1.1309 B.97 C.6 1.1310 B.98 C.6 1.1311 B.99 C.61.1312 B.100 C.6 1.1313 B.101 C.6 1.1314 B.102 C.6 1.1315 B.103 C.61.1316 B.104 C.6 1.1317 B.105 C.6 1.1318 B.106 C.6 1.1319 B.107 C.61.1320 B.108 C.6 1.1321 B.109 C.6 1.1322 B.110 C.6 1.1323 B.111 C.61.1324 B.112 C.6 1.1325 B.113 C.6 1.1326 B.114 C.6 1.1327 B.115 C.61.1328 B.116 C.6 1.1329 B.117 C.6 1.1330 B.118 C.6 1.1331 B.119 C.61.1332 B.120 C.6 1.1333 B.121 C.6 1.1334 B.122 C.6 1.1335 B.123 C.61.1336 B.124 C.6 1.1337 B.125 C.6 1.1338 B.126 C.6 1.1339 B.127 C.61.1340 B.128 C.6 1.1341 B.129 C.6 1.1342 B.130 C.6 1.1343 B.131 C.61.1344 B.132 C.6 1.1345 B.133 C.6 1.1346 B.134 C.6 1.1347 B.135 C.61.1348 B.136 C.6 1.1349 B.137 C.6 1.1350 B.138 C.6 1.1351 B.139 C.61.1352 B.140 C.6 1.1353 B.141 C.6 1.1354 B.142 C.6 1.1355 B.143 C.61.1356 B.144 C.6 1.1357 B.145 C.6 1.1358 B.146 C.6 1.1359 B.147 C.61.1360 B.148 C.6 1.1361 B.149 C.6 1.1362 B.150 C.6 1.1363 B.151 C.61.1364 B.152 C.6 1.1365 B.153 C.6 1.1366 B.154 C.6 1.1367 B.155 C.61.1368 B.156 C.6 1.1369 B.157 C.6 1.1370 B.158 C.6 1.1371 B.159 C.61.1372 B.160 C.6 1.1373 B.161 C.6 1.1374 B.162 C.6 1.1375 B.163 C.61.1376 B.164 C.6 1.1377 B.165 C.6 1.1378 B.166 C.6 1.1379 B.167 C.61.1380 B.168 C.6 1.1381 B.169 C.6 1.1382 B.170 C.6 1.1383 B.171 C.61.1384 B.172 C.6 1.1385 B.173 C.6 1.1386 B.174 C.6 1.1387 B.175 C.61.1388 B.176 C.6 1.1389 B.177 C.6 1.1390 B.178 C.6 1.1391 B.179 C.61.1392 B.180 C.6 1.1393 B.181 C.6 1.1394 B.182 C.6 1.1395 B.183 C.61.1396 B.184 C.6 1.1397 B.185 C.6 1.1398 B.186 C.6 1.1399 B.187 C.61.1400 B.188 C.6 1.1401 B.189 C.6 1.1402 B.190 C.6 1.1403 B.191 C.61.1404 B.192 C.6 1.1405 B.193 C.6 1.1406 B.194 C.6 1.1407 B.195 C.61.1408 B.196 C.6 1.1409 B.197 C.6 1.1410 B.198 C.6 1.1411 B.199 C.61.1412 B.200 C.6 1.1413 B.201 C.6 1.1414 B.202 C.6 1.1415 B.1 C.7 1.1416B.2 C.7 1.1417 B.3 C.7 1.1418 B.4 C.7 1.1419 B.5 C.7 1.1420 B.6 C.71.1421 B.7 C.7 1.1422 B.8 C.7 1.1423 B.9 C.7 1.1424 B.10 C.7 1.1425 B.11C.7 1.1426 B.12 C.7 1.1427 B.13 C.7 1.1428 B.14 C.7 1.1429 B.15 C.71.1430 B.16 C.7 1.1431 B.17 C.7 1.1432 B.18 C.7 1.1433 B.19 C.7 1.1434B.20 C.7 1.1435 B.21 C.7 1.1436 B.22 C.7 1.1437 B.23 C.7 1.1438 B.24 C.71.1439 B.25 C.7 1.1440 B.26 C.7 1.1441 B.27 C.7 1.1442 B.28 C.7 1.1443B.29 C.7 1.1444 B.30 C.7 1.1445 B.31 C.7 1.1446 B.32 C.7 1.1447 B.33 C.71.1448 B.34 C.7 1.1449 B.35 C.7 1.1450 B.36 C.7 1.1451 B.37 C.7 1.1452B.38 C.7 1.1453 B.39 C.7 1.1454 B.40 C.7 1.1455 B.41 C.7 1.1456 B.42 C.71.1457 B.43 C.7 1.1458 B.44 C.7 1.1459 B.45 C.7 1.1460 B.46 C.7 1.1461B.47 C.7 1.1462 B.48 C.7 1.1463 B.49 C.7 1.1464 B.50 C.7 1.1465 B.51 C.71.1466 B.52 C.7 1.1467 B.53 C.7 1.1468 B.54 C.7 1.1469 B.55 C.7 1.1470B.56 C.7 1.1471 B.57 C.7 1.1472 B.58. C.7 1.1473 B.59 C.7 1.1474 B.60C.7 1.1475 B.61 C.7 1.1476 B.62 C.7 1.1477 B.63 C.7 1.1478 B.64 C.71.1479 B.65 C.7 1.1480 B.66 C.7 1.1481 B.67 C.7 1.1482 B.68 C.7 1.1483B.69 C.7 1.1484 B.70 C.7 1.1485 B.71 C.7 1.1486 B.72 C.7 1.1487 B.73 C.71.1488 B.74 C.7 1.1489 B.75 C.7 1.1490 B.76 C.7 1.1491 B.77 C.7 1.1492B.78 C.7 1.1493 B.79 C.7 1.1494 B.80 C.7 1.1495 B.81 C.7 1.1496 B.82 C.71.1497 B.83 C.7 1.1498 B.84 C.7 1.1499 B.85 C.7 1.1500 B.86 C.7 1.1501B.87 C.7 1.1502 B.88 C.7 1.1503 B.89 C.7 1.1504 B.90 C.7 1.1505 B.91 C.71.1506 B.92 C.7 1.1507 B.93 C.7 1.1508 B.94 C.7 1.1509 B.95 C.7 1.1510B.96 C.7 1.1511 B.97 C.7 1.1512 B.98 C.7 1.1513 B.99 C.7 1.1514 B.100C.7 1.1515 B.101 C.7 1.1516 B.102 C.7 1.1517 B.103 C.7 1.1518 B.104 C.71.1519 B.105 C.7 1.1520 B.106 C.7 1.1521 B.107 C.7 1.1522 B.108 C.71.1523 B.109 C.7 1.1524 B.110 C.7 1.1525 B.111 C.7 1.1526 B.112 C.71.1527 B.113 C.7 1.1528 B.114 C.7 1.1529 B.115 C.7 1.1530 B.116 C.71.1531 B.117 C.7 1.1532 B.118 C.7 1.1533 B.119 C.7 1.1534 B.120 C.71.1535 B.121 C.7 1.1536 B.122 C.7 1.1537 B.123 C.7 1.1538 B.124 C.71.1539 B.125 C.7 1.1540 B.126 C.7 1.1541 B.127 C.7 1.1542 B.128 C.71.1543 B.129 C.7 1.1544 B.130 C.7 1.1545 B.131 C.7 1.1546 B.132 C.71.1547 B.133 C.7 1.1548 B.134 C.7 1.1549 B.135 C.7 1.1550 B.136 C.71.1551 B.137 C.7 1.1552 B.138 C.7 1.1553 B.139 C.7 1.1554 B.140 C.71.1555 B.141 C.7 1.1556 B.142 C.7 1.1557 B.143 C.7 1.1558 B.144 C.71.1559 B.145 C.7 1.1560 B.146 C.7 1.1561 B.147 C.7 1.1562 B.148 C.71.1563 B.149 C.7 1.1564 B.150 C.7 1.1565 B.151 C.7 1.1566 B.152 C.71.1567 B.153 C.7 1.1568 B.154 C.7 1.1569 B.155 C.7 1.1570 B.156 C.71.1571 B.157 C.7 1.1572 B.158 C.7 1.1573 B.159 C.7 1.1574 B.160 C.71.1575 B.161 C.7 1.1576 B.162 C.7 1.1577 B.163 C.7 1.1578 B.164 C.71.1579 B.165 C.7 1.1580 B.166 C.7 1.1581 B.167 C.7 1.1582 B.168 C.71.1583 B.169 C.7 1.1584 B.170 C.7 1.1585 B.171 C.7 1.1586 B.172 C.71.1587 B.173 C.7 1.1588 B.174 C.7 1.1589 B.175 C.7 1.1590 B.176 C.71.1591 B.177 C.7 1.1592 B.178 C.7 1.1593 B.179 C.7 1.1594 B.180 C.71.1595 B.181 C.7 1.1596 B.182 C.7 1.1597 B.183 C.7 1.1598 B.184 C.71.1599 B.185 C.7 1.1600 B.186 C.7 1.1601 B.187 C.7 1.1602 B.188 C.71.1603 B.189 C.7 1.1604 B.190 C.7 1.1605 B.191 C.7 1.1606 B.192 C.71.1607 B.193 C.7 1.1608 B.194 C.7 1.1609 B.195 C.7 1.1610 B.196 C.71.1611 B.197 C.7 1.1612 B.198 C.7 1.1613 B.199 C.7 1.1614 B.200 C.71.1615 B.201 C.7 1.1616 B.202 C.7 1.1617 B.1 C.8 1.1618 B.2 C.8 1.1619B.3 C.8 1.1620 B.4 C.8 1.1621 B.5 C.8 1.1622 B.6 C.8 1.1623 B.7 C.81.1624 B.8 C.8 1.1625 B.9 C.8 1.1626 B.10 C.8 1.1627 B.11 C.8 1.1628B.12 C.8 1.1629 B.13 C.8 1.1630 B.14 C.8 1.1631 B.15 C.8 1.1632 B.16 C.81.1633 B.17 C.8 1.1634 B.18 C.8 1.1635 B.19 C.8 1.1636 B.20 C.8 1.1637B.21 C.8 1.1638 B.22 C.8 1.1639 B.23 C.8 1.1640 B.24 C.8 1.1641 B.25 C.81.1642 B.26 C.8 1.1643 B.27 C.8 1.1644 B.28 C.8 1.1645 B.29 C.8 1.1646B.30 C.8 1.1647 B.31 C.8 1.1648 B.32 C.8 1.1649 B.33 C.8 1.1650 B.34 C.81.1651 B.35 C.8 1.1652 B.36 C.8 1.1653 B.37 C.8 1.1654 B.38 C.8 1.1655B.39 C.8 1.1656 B.40 C.8 1.1657 B.41 C.8 1.1658 B.42 C.8 1.1659 B.43 C.81.1660 B.44 C.8 1.1661 B.45 C.8 1.1662 B.46 C.8 1.1663 B.47 C.8 1.1664B.48 C.8 1.1665 B.49 C.8 1.1666 B.50 C.8 1.1667 B.51 C.8 1.1668 B.52 C.81.1669 B.53 C.8 1.1670 B.54 C.8 1.1671 B.55 C.8 1.1672 B.56 C.8 1.1673B.57 C.8 1.1674 B.58. C.8 1.1675 B.59 C.8 1.1676 B.60 C.8 1.1677 B.61C.8 1.1678 B.62 C.8 1.1679 B.63 C.8 1.1680 B.64 C.8 1.1681 B.65 C.81.1682 B.66 C.8 1.1683 B.67 C.8 1.1684 B.68 C.8 1.1685 B.69 C.8 1.1686B.70 C.8 1.1687 B.71 C.8 1.1688 B.72 C.8 1.1689 B.73 C.8 1.1690 B.74 C.81.1691 B.75 C.8 1.1692 B.76 C.8 1.1693 B.77 C.8 1.1694 B.78 C.8 1.1695B.79 C.8 1.1696 B.80 C.8 1.1697 B.81 C.8 1.1698 B.82 C.8 1.1699 B.83 C.81.1700 B.84 C.8 1.1701 B.85 C.8 1.1702 B.86 C.8 1.1703 B.87 C.8 1.1704B.88 C.8 1.1705 B.89 C.8 1.1706 B.90 C.8 1.1707 B.91 C.8 1.1708 B.92 C.81.1709 B.93 C.8 1.1710 B.94 C.8 1.1711 B.95 C.8 1.1712 B.96 C.8 1.1713B.97 C.8 1.1714 B.98 C.8 1.1715 B.99 C.8 1.1716 B.100 C.8 1.1717 B.101C.8 1.1718 B.102 C.8 1.1719 B.103 C.8 1.1720 B.104 C.8 1.1721 B.105 C.81.1722 B.106 C.8 1.1723 B.107 C.8 1.1724 B.108 C.8 1.1725 B.109 C.81.1726 B.110 C.8 1.1727 B.111 C.8 1.1728 B.112 C.8 1.1729 B.113 C.81.1730 B.114 C.8 1.1731 B.115 C.8 1.1732 B.116 C.8 1.1733 B.117 C.81.1734 B.118 C.8 1.1735 B.119 C.8 1.1736 B.120 C.8 1.1737 B.121 C.81.1738 B.122 C.8 1.1739 B.123 C.8 1.1740 B.124 C.8 1.1741 B.125 C.81.1742 B.126 C.8 1.1743 B.127 C.8 1.1744 B.128 C.8 1.1745 B.129 C.81.1746 B.130 C.8 1.1747 B.131 C.8 1.1748 B.132 C.8 1.1749 B.133 C.81.1750 B.134 C.8 1.1751 B.135 C.8 1.1752 B.136 C.8 1.1753 B.137 C.81.1754 B.138 C.8 1.1755 B.139 C.8 1.1756 B.140 C.8 1.1757 B.141 C.81.1758 B.142 C.8 1.1759 B.143 C.8 1.1760 B.144 C.8 1.1761 B.145 C.81.1762 B.146 C.8 1.1763 B.147 C.8 1.1764 B.148 C.8 1.1765 B.149 C.81.1766 B.150 C.8 1.1767 B.151 C.8 1.1768 B.152 C.8 1.1769 B.153 C.81.1770 B.154 C.8 1.1771 B.155 C.8 1.1772 B.156 C.8 1.1773 B.157 C.81.1774 B.158 C.8 1.1775 B.159 C.8 1.1776 B.160 C.8 1.1777 B.161 C.81.1778 B.162 C.8 1.1779 B.163 C.8 1.1780 B.164 C.8 1.1781 B.165 C.81.1782 B.166 C.8 1.1783 B.167 C.8 1.1784 B.168 C.8 1.1785 B.169 C.81.1786 B.170 C.8 1.1787 B.171 C.8 1.1788 B.172 C.8 1.1789 B.173 C.81.1790 B.174 C.8 1.1791 B.175 C.8 1.1792 B.176 C.8 1.1793 B.177 C.81.1794 B.178 C.8 1.1795 B.179 C.8 1.1796 B.180 C.8 1.1797 B.181 C.81.1798 B.182 C.8 1.1799 B.183 C.8 1.1800 B.184 C.8 1.1801 B.185 C.81.1802 B.186 C.8 1.1803 B.187 C.8 1.1804 B.188 C.8 1.1805 B.189 C.81.1806 B.190 C.8 1.1807 B.191 C.8 1.1808 B.192 C.8 1.1809 B.193 C.81.1810 B.194 C.8 1.1811 B.195 C.8 1.1812 B.196 C.8 1.1813 B.197 C.81.1814 B.198 C.8 1.1815 B.199 C.8 1.1816 B.200 C.8 1.1817 B.201 C.81.1818 B.202 C.8 1.1819 B.1 C.9 1.1820 B.2 C.9 1.1821 B.3 C.9 1.1822 B.4C.9 1.1823 B.5 C.9 1.1824 B.6 C.9 1.1825 B.7 C.9 1.1826 B.8 C.9 1.1827B.9 C.9 1.1828 B.10 C.9 1.1829 B.11 C.9 1.1830 B.12 C.9 1.1831 B.13 C.91.1832 B.14 C.9 1.1833 B.15 C.9 1.1834 B.16 C.9 1.1835 B.17 C.9 1.1836B.18 C.9 1.1837 B.19 C.9 1.1838 B.20 C.9 1.1839 B.21 C.9 1.1840 B.22 C.91.1841 B.23 C.9 1.1842 B.24 C.9 1.1843 B.25 C.9 1.1844 B.26 C.9 1.1845B.27 C.9 1.1846 B.28 C.9 1.1847 B.29 C.9 1.1848 B.30 C.9 1.1849 B.31 C.91.1850 B.32 C.9 1.1851 B.33 C.9 1.1852 B.34 C.9 1.1853 B.35 C.9 1.1854B.36 C.9 1.1855 B.37 C.9 1.1856 B.38 C.9 1.1857 B.39 C.9 1.1858 B.40 C.91.1859 B.41 C.9 1.1860 B.42 C.9 1.1861 B.43 C.9 1.1862 B.44 C.9 1.1863B.45 C.9 1.1864 B.46 C.9 1.1865 B.47 C.9 1.1866 B.48 C.9 1.1867 B.49 C.91.1868 B.50 C.9 1.1869 B.51 C.9 1.1870 B.52 C.9 1.1871 B.53 C.9 1.1872B.54 C.9 1.1873 B.55 C.9 1.1874 B.56 C.9 1.1875 B.57 C.9 1.1876 B.58.C.9 1.1877 B.59 C.9 1.1878 B.60 C.9 1.1879 B.61 C.9 1.1880 B.62 C.91.1881 B.63 C.9 1.1882 B.64 C.9 1.1883 B.65 C.9 1.1884 B.66 C.9 1.1885B.67 C.9 1.1886 B.68 C.9 1.1887 B.69 C.9 1.1888 B.70 C.9 1.1889 B.71 C.91.1890 B.72 C.9 1.1891 B.73 C.9 1.1892 B.74 C.9 1.1893 B.75 C.9 1.1894B.76 C.9 1.1895 B.77 C.9 1.1896 B.78 C.9 1.1897 B.79 C.9 1.1898 B.80 C.91.1899 B.81 C.9 1.1900 B.82 C.9 1.1901 B.83 C.9 1.1902 B.84 C.9 1.1903B.85 C.9 1.1904 B.86 C.9 1.1905 B.87 C.9 1.1906 B.88 C.9 1.1907 B.89 C.91.1908 B.90 C.9 1.1909 B.91 C.9 1.1910 B.92 C.9 1.1911 B.93 C.9 1.1912B.94 C.9 1.1913 B.95 C.9 1.1914 B.96 C.9 1.1915 B.97 C.9 1.1916 B.98 C.91.1917 B.99 C.9 1.1918 B.100 C.9 1.1919 B.101 C.9 1.1920 B.102 C.91.1921 B.103 C.9 1.1922 B.104 C.9 1.1923 B.105 C.9 1.1924 B.106 C.91.1925 B.107 C.9 1.1926 B.108 C.9 1.1927 B.109 C.9 1.1928 B.110 C.91.1929 B.111 C.9 1.1930 B.112 C.9 1.1931 B.113 C.9 1.1932 B.114 C.91.1933 B.115 C.9 1.1934 B.116 C.9 1.1935 B.117 C.9 1.1936 B.118 C.91.1937 B.119 C.9 1.1938 B.120 C.9 1.1939 B.121 C.9 1.1940 B.122 C.91.1941 B.123 C.9 1.1942 B.124 C.9 1.1943 B.125 C.9 1.1944 B.126 C.91.1945 B.127 C.9 1.1946 B.128 C.9 1.1947 B.129 C.9 1.1948 B.130 C.91.1949 B.131 C.9 1.1950 B.132 C.9 1.1951 B.133 C.9 1.1952 B.134 C.91.1953 B.135 C.9 1.1954 B.136 C.9 1.1955 B.137 C.9 1.1956 B.138 C.91.1957 B.139 C.9 1.1958 B.140 C.9 1.1959 B.141 C.9 1.1960 B.142 C.91.1961 B.143 C.9 1.1962 B.144 C.9 1.1963 B.145 C.9 1.1964 B.146 C.91.1965 B.147 C.9 1.1966 B.148 C.9 1.1967 B.149 C.9 1.1968 B.150 C.91.1969 B.151 C.9 1.1970 B.152 C.9 1.1971 B.153 C.9 1.1972 B.154 C.91.1973 B.155 C.9 1.1974 B.156 C.9 1.1975 B.157 C.9 1.1976 B.158 C.91.1977 B.159 C.9 1.1978 B.160 C.9 1.1979 B.161 C.9 1.1980 B.162 C.91.1981 B.163 C.9 1.1982 B.164 C.9 1.1983 B.165 C.9 1.1984 B.166 C.91.1985 B.167 C.9 1.1986 B.168 C.9 1.1987 B.169 C.9 1.1988 B.170 C.91.1989 B.171 C.9 1.1990 B.172 C.9 1.1991 B.173 C.9 1.1992 B.174 C.91.1993 B.175 C.9 1.1994 B.176 C.9 1.1995 B.177 C.9 1.1996 B.178 C.91.1997 B.179 C.9 1.1998 B.180 C.9 1.1999 B.181 C.9 1.2000 B.182 C.91.2001 B.183 C.9 1.2002 B.184 C.9 1.2003 B.185 C.9 1.2004 B.186 C.91.2005 B.187 C.9 1.2006 B.188 C.9 1.2007 B.189 C.9 1.2008 B.190 C.91.2009 B.191 C.9 1.2010 B.192 C.9 1.2011 B.193 C.9 1.2012 B.194 C.91.2013 B.195 C.9 1.2014 B.196 C.9 1.2015 B.197 C.9 1.2016 B.198 C.91.2017 B.199 C.9 1.2018 B.200 C.9 1.2019 B.201 C.9 1.2020 B.202 C.91.2021 B.1 C.10 1.2022 B.2 C.10 1.2023 B.3 C.10 1.2024 B.4 C.10 1.2025B.5 C.10 1.2026 B.6 C.10 1.2027 B.7 C.10 1.2028 B.8 C.10 1.2029 B.9 C.101.2030 B.10 C.10 1.2031 B.11 C.10 1.2032 B.12 C.10 1.2033 B.13 C.101.2034 B.14 C.10 1.2035 B.15 C.10 1.2036 B.16 C.10 1.2037 B.17 C.101.2038 B.18 C.10 1.2039 B.19 C.10 1.2040 B.20 C.10 1.2041 B.21 C.101.2042 B.22 C.10 1.2043 B.23 C.10 1.2044 B.24 C.10 1.2045 B.25 C.101.2046 B.26 C.10 1.2047 B.27 C.10 1.2048 B.28 C.10 1.2049 B.29 C.101.2050 B.30 C.10 1.2051 B.31 C.10 1.2052 B.32 C.10 1.2053 B.33 C.101.2054 B.34 C.10 1.2055 B.35 C.10 1.2056 B.36 C.10 1.2057 B.37 C.101.2058 B.38 C.10 1.2059 B.39 C.10 1.2060 B.40 C.10 1.2061 B.41 C.101.2062 B.42 C.10 1.2063 B.43 C.10 1.2064 B.44 C.10 1.2065 B.45 C.101.2066 B.46 C.10 1.2067 B.47 C.10 1.2068 B.48 C.10 1.2069 B.49 C.101.2070 B.50 C.10 1.2071 B.51 C.10 1.2072 B.52 C.10 1.2073 B.53 C.101.2074 B.54 C.10 1.2075 B.55 C.10 1.2076 B.56 C.10 1.2077 B.57 C.101.2078 B.58. C.10 1.2079 B.59 C.10 1.2080 B.60 C.10 1.2081 B.61 C.101.2082 B.62 C.10 1.2083 B.63 C.10 1.2084 B.64 C.10 1.2085 B.65 C.101.2086 B.66 C.10 1.2087 B.67 C.10 1.2088 B.68 C.10 1.2089 B.69 C.101.2090 B.70 C.10 1.2091 B.71 C.10 1.2092 B.72 C.10 1.2093 B.73 C.101.2094 B.74 C.10 1.2095 B.75 C.10 1.2096 B.76 C.10 1.2097 B.77 C.101.2098 B.78 C.10 1.2099 B.79 C.10 1.2100 B.80 C.10 1.2101 B.81 C.101.2102 B.82 C.10 1.2103 B.83 C.10 1.2104 B.84 C.10 1.2105 B.85 C.101.2106 B.86 C.10 1.2107 B.87 C.10 1.2108 B.88 C.10 1.2109 B.89 C.101.2110 B.90 C.10 1.2111 B.91 C.10 1.2112 B.92 C.10 1.2113 B.93 C.101.2114 B.94 C.10 1.2115 B.95 C.10 1.2116 B.96 C.10 1.2117 B.97 C.101.2118 B.98 C.10 1.2119 B.99 C.10 1.2120 B.100 C.10 1.2121 B.101 C.101.2122 B.102 C.10 1.2123 B.103 C.10 1.2124 B.104 C.10 1.2125 B.105 C.101.2126 B.106 C.10 1.2127 B.107 C.10 1.2128 B.108 C.10 1.2129 B.109 C.101.2130 B.110 C.10 1.2131 B.111 C.10 1.2132 B.112 C.10 1.2133 B.113 C.101.2134 B.114 C.10 1.2135 B.115 C.10 1.2136 B.116 C.10 1.2137 B.117 C.101.2138 B.118 C.10 1.2139 B.119 C.10 1.2140 B.120 C.10 1.2141 B.121 C.101.2142 B.122 C.10 1.2143 B.123 C.10 1.2144 B.124 C.10 1.2145 B.125 C.101.2146 B.126 C.10 1.2147 B.127 C.10 1.2148 B.128 C.10 1.2149 B.129 C.101.2150 B.130 C.10 1.2151 B.131 C.10 1.2152 B.132 C.10 1.2153 B.133 C.101.2154 B.134 C.10 1.2155 B.135 C.10 1.2156 B.136 C.10 1.2157 B.137 C.101.2158 B.138 C.10 1.2159 B.139 C.10 1.2160 B.140 C.10 1.2161 B.141 C.101.2162 B.142 C.10 1.2163 B.143 C.10 1.2164 B.144 C.10 1.2165 B.145 C.101.2166 B.146 C.10 1.2167 B.147 C.10 1.2168 B.148 C.10 1.2169 B.149 C.101.2170 B.150 C.10 1.2171 B.151 C.10 1.2172 B.152 C.10 1.2173 B.153 C.101.2174 B.154 C.10 1.2175 B.155 C.10 1.2176 B.156 C.10 1.2177 B.157 C.101.2178 B.158 C.10 1.2179 B.159 C.10 1.2180 B.160 C.10 1.2181 B.161 C.101.2182 B.162 C.10 1.2183 B.163 C.10 1.2184 B.164 C.10 1.2185 B.165 C.101.2186 B.166 C.10 1.2187 B.167 C.10 1.2188 B.168 C.10 1.2189 B.169 C.101.2190 B.170 C.10 1.2191 B.171 C.10 1.2192 B.172 C.10 1.2193 B.173 C.101.2194 B.174 C.10 1.2195 B.175 C.10 1.2196 B.176 C.10 1.2197 B.177 C.101.2198 B.178 C.10 1.2199 B.179 C.10 1.2200 B.180 C.10 1.2201 B.181 C.101.2202 B.182 C.10 1.2203 B.183 C.10 1.2204 B.184 C.10 1.2205 B.185 C.101.2206 B.186 C.10 1.2207 B.187 C.10 1.2208 B.188 C.10 1.2209 B.189 C.101.2210 B.190 C.10 1.2211 B.191 C.10 1.2212 B.192 C.10 1.2213 B.193 C.101.2214 B.194 C.10 1.2215 B.195 C.10 1.2216 B.196 C.10 1.2217 B.197 C.101.2218 B.198 C.10 1.2219 B.199 C.10 1.2220 B.200 C.10 1.2221 B.201 C.101.2222 B.202 C.10 1.2223 B.1 C.11 1.2224 B.2 C.11 1.2225 B.3 C.11 1.2226B.4 C.11 1.2227 B.5 C.11 1.2228 B.6 C.11 1.2229 B.7 C.11 1.2230 B.8 C.111.2231 B.9 C.11 1.2232 B.10 C.11 1.2233 B.11 C.11 1.2234 B.12 C.111.2235 B.13 C.11 1.2236 B.14 C.11 1.2237 B.15 C.11 1.2238 B.16 C.111.2239 B.17 C.11 1.2240 B.18 C.11 1.2241 B.19 C.11 1.2242 B.20 C.111.2243 B.21 C.11 1.2244 B.22 C.11 1.2245 B.23 C.11 1.2246 B.24 C.111.2247 B.25 C.11 1.2248 B.26 C.11 1.2249 B.27 C.11 1.2250 B.28 C.111.2251 B.29 C.11 1.2252 B.30 C.11 1.2253 B.31 C.11 1.2254 B.32 C.111.2255 B.33 C.11 1.2256 B.34 C.11 1.2257 B.35 C.11 1.2258 B.36 C.111.2259 B.37 C.11 1.2260 B.38 C.11 1.2261 B.39 C.11 1.2262 B.40 C.111.2263 B.41 C.11 1.2264 B.42 C.11 1.2265 B.43 C.11 1.2266 B.44 C.111.2267 B.45 C.11 1.2268 B.46 C.11 1.2269 B.47 C.11 1.2270 B.48 C.111.2271 B.49 C.11 1.2272 B.50 C.11 1.2273 B.51 C.11 1.2274 B.52 C.111.2275 B.53 C.11 1.2276 B.54 C.11 1.2277 B.55 C.11 1.2278 B.56 C.111.2279 B.57 C.11 1.2280 B.58. C.11 1.2281 B.59 C.11 1.2282 B.60 C.111.2283 B.61 C.11 1.2284 B.62 C.11 1.2285 B.63 C.11 1.2286 B.64 C.111.2287 B.65 C.11 1.2288 B.66 C.11 1.2289 B.67 C.11 1.2290 B.68 C.111.2291 B.69 C.11 1.2292 B.70 C.11 1.2293 B.71 C.11 1.2294 B.72 C.111.2295 B.73 C.11 1.2296 B.74 C.11 1.2297 B.75 C.11 1.2298 B.76 C.111.2299 B.77 C.11 1.2300 B.78 C.11 1.2301 B.79 C.11 1.2302 B.80 C.111.2303 B.81 C.11 1.2304 B.82 C.11 1.2305 B.83 C.11 1.2306 B.84 C.111.2307 B.85 C.11 1.2308 B.86 C.11 1.2309 B.87 C.11 1.2310 B.88 C.111.2311 B.89 C.11 1.2312 B.90 C.11 1.2313 B.91 C.11 1.2314 B.92 C.111.2315 B.93 C.11 1.2316 B.94 C.11 1.2317 B.95 C.11 1.2318 B.96 C.111.2319 B.97 C.11 1.2320 B.98 C.11 1.2321 B.99 C.11 1.2322 B.100 C.111.2323 B.101 C.11 1.2324 B.102 C.11 1.2325 B.103 C.11 1.2326 B.104 C.111.2327 B.105 C.11 1.2328 B.106 C.11 1.2329 B.107 C.11 1.2330 B.108 C.111.2331 B.109 C.11 1.2332 B.110 C.11 1.2333 B.111 C.11 1.2334 B.112 C.111.2335 B.113 C.11 1.2336 B.114 C.11 1.2337 B.115 C.11 1.2338 B.116 C.111.2339 B.117 C.11 1.2340 B.118 C.11 1.2341 B.119 C.11 1.2342 B.120 C.111.2343 B.121 C.11 1.2344 B.122 C.11 1.2345 B.123 C.11 1.2346 B.124 C.111.2347 B.125 C.11 1.2348 B.126 C.11 1.2349 B.127 C.11 1.2350 B.128 C.111.2351 B.129 C.11 1.2352 B.130 C.11 1.2353 B.131 C.11 1.2354 B.132 C.111.2355 B.133 C.11 1.2356 B.134 C.11 1.2357 B.135 C.11 1.2358 B.136 C.111.2359 B.137 C.11 1.2360 B.138 C.11 1.2361 B.139 C.11 1.2362 B.140 C.111.2363 B.141 C.11 1.2364 B.142 C.11 1.2365 B.143 C.11 1.2366 B.144 C.111.2367 B.145 C.11 1.2368 B.146 C.11 1.2369 B.147 C.11 1.2370 B.148 C.111.2371 B.149 C.11 1.2372 B.150 C.11 1.2373 B.151 C.11 1.2374 B.152 C.111.2375 B.153 C.11 1.2376 B.154 C.11 1.2377 B.155 C.11 1.2378 B.156 C.111.2379 B.157 C.11 1.2380 B.158 C.11 1.2381 B.159 C.11 1.2382 B.160 C.111.2383 B.161 C.11 1.2384 B.162 C.11 1.2385 B.163 C.11 1.2386 B.164 C.111.2387 B.165 C.11 1.2388 B.166 C.11 1.2389 B.167 C.11 1.2390 B.168 C.111.2391 B.169 C.11 1.2392 B.170 C.11 1.2393 B.171 C.11 1.2394 B.172 C.111.2395 B.173 C.11 1.2396 B.174 C.11 1.2397 B.175 C.11 1.2398 B.176 C.111.2399 B.177 C.11 1.2400 B.178 C.11 1.2401 B.179 C.11 1.2402 B.180 C.111.2403 B.181 C.11 1.2404 B.182 C.11 1.2405 B.183 C.11 1.2406 B.184 C.111.2407 B.185 C.11 1.2408 B.186 C.11 1.2409 B.187 C.11 1.2410 B.188 C.111.2411 B.189 C.11 1.2412 B.190 C.11 1.2413 B.191 C.11 1.2414 B.192 C.111.2415 B.193 C.11 1.2416 B.194 C.11 1.2417 B.195 C.11 1.2418 B.196 C.111.2419 B.197 C.11 1.2420 B.198 C.11 1.2421 B.199 C.11 1.2422 B.200 C.111.2423 B.201 C.11 1.2424 B.202 C.11 1.2425 B.1 C.12 1.2426 B.2 C.121.2427 B.3 C.12 1.2428 B.4 C.12 1.2429 B.5 C.12 1.2430 B.6 C.12 1.2431B.7 C.12 1.2432 B.8 C.12 1.2433 B.9 C.12 1.2434 B.10 C.12 1.2435 B.11C.12 1.2436 B.12 C.12 1.2437 B.13 C.12 1.2438 B.14 C.12 1.2439 B.15 C.121.2440 B.16 C.12 1.2441 B.17 C.12 1.2442 B.18 C.12 1.2443 B.19 C.121.2444 B.20 C.12 1.2445 B.21 C.12 1.2446 B.22 C.12 1.2447 B.23 C.121.2448 B.24 C.12 1.2449 B.25 C.12 1.2450 B.26 C.12 1.2451 B.27 C.121.2452 B.28 C.12 1.2453 B.29 C.12 1.2454 B.30 C.12 1.2455 B.31 C.121.2456 B.32 C.12 1.2457 B.33 C.12 1.2458 B.34 C.12 1.2459 B.35 C.121.2460 B.36 C.12 1.2461 B.37 C.12 1.2462 B.38 C.12 1.2463 B.39 C.121.2464 B.40 C.12 1.2465 B.41 C.12 1.2466 B.42 C.12 1.2467 B.43 C.121.2468 B.44 C.12 1.2469 B.45 C.12 1.2470 B.46 C.12 1.2471 B.47 C.121.2472 B.48 C.12 1.2473 B.49 C.12 1.2474 B.50 C.12 1.2475 B.51 C.121.2476 B.52 C.12 1.2477 B.53 C.12 1.2478 B.54 C.12 1.2479 B.55 C.121.2480 B.56 C.12 1.2481 B.57 C.12 1.2482 B.58. C.12 1.2483 B.59 C.121.2484 B.60 C.12 1.2485 B.61 C.12 1.2486 B.62 C.12 1.2487 B.63 C.121.2488 B.64 C.12 1.2489 B.65 C.12 1.2490 B.66 C.12 1.2491 B.67 C.121.2492 B.68 C.12 1.2493 B.69 C.12 1.2494 B.70 C.12 1.2495 B.71 C.121.2496 B.72 C.12 1.2497 B.73 C.12 1.2498 B.74 C.12 1.2499 B.75 C.121.2500 B.76 C.12 1.2501 B.77 C.12 1.2502 B.78 C.12 1.2503 B.79 C.121.2504 B.80 C.12 1.2505 B.81 C.12 1.2506 B.82 C.12 1.2507 B.83 C.121.2508 B.84 C.12 1.2509 B.85 C.12 1.2510 B.86 C.12 1.2511 B.87 C.121.2512 B.88 C.12 1.2513 B.89 C.12 1.2514 B.90 C.12 1.2515 B.91 C.121.2516 B.92 C.12 1.2517 B.93 C.12 1.2518 B.94 C.12 1.2519 B.95 C.121.2520 B.96 C.12 1.2521 B.97 C.12 1.2522 B.98 C.12 1.2523 B.99 C.121.2524 B.100 C.12 1.2525 B.101 C.12 1.2526 B.102 C.12 1.2527 B.103 C.121.2528 B.104 C.12 1.2529 B.105 C.12 1.2530 B.106 C.12 1.2531 B.107 C.121.2532 B.108 C.12 1.2533 B.109 C.12 1.2534 B.110 C.12 1.2535 B.111 C.121.2536 B.112 C.12 1.2537 B.113 C.12 1.2538 B.114 C.12 1.2539 B.115 C.121.2540 B.116 C.12 1.2541 B.117 C.12 1.2542 B.118 C.12 1.2543 B.119 C.121.2544 B.120 C.12 1.2545 B.121 C.12 1.2546 B.122 C.12 1.2547 B.123 C.121.2548 B.124 C.12 1.2549 B.125 C.12 1.2550 B.126 C.12 1.2551 B.127 C.121.2552 B.128 C.12 1.2553 B.129 C.12 1.2554 B.130 C.12 1.2555 B.131 C.121.2556 B.132 C.12 1.2557 B.133 C.12 1.2558 B.134 C.12 1.2559 B.135 C.121.2560 B.136 C.12 1.2561 B.137 C.12 1.2562 B.138 C.12 1.2563 B.139 C.121.2564 B.140 C.12 1.2565 B.141 C.12 1.2566 B.142 C.12 1.2567 B.143 C.121.2568 B.144 C.12 1.2569 B.145 C.12 1.2570 B.146 C.12 1.2571 B.147 C.121.2572 B.148 C.12 1.2573 B.149 C.12 1.2574 B.150 C.12 1.2575 B.151 C.121.2576 B.152 C.12 1.2577 B.153 C.12 1.2578 B.154 C.12 1.2579 B.155 C.121.2580 B.156 C.12 1.2581 B.157 C.12 1.2582 B.158 C.12 1.2583 B.159 C.121.2584 B.160 C.12 1.2585 B.161 C.12 1.2586 B.162 C.12 1.2587 B.163 C.121.2588 B.164 C.12 1.2589 B.165 C.12 1.2590 B.166 C.12 1.2591 B.167 C.121.2592 B.168 C.12 1.2593 B.169 C.12 1.2594 B.170 C.12 1.2595 B.171 C.121.2596 B.172 C.12 1.2597 B.173 C.12 1.2598 B.174 C.12 1.2599 B.175 C.121.2600 B.176 C.12 1.2601 B.177 C.12 1.2602 B.178 C.12 1.2603 B.179 C.121.2604 B.180 C.12 1.2605 B.181 C.12 1.2606 B.182 C.12 1.2607 B.183 C.121.2608 B.184 C.12 1.2609 B.185 C.12 1.2610 B.186 C.12 1.2611 B.187 C.121.2612 B.188 C.12 1.2613 B.189 C.12 1.2614 B.190 C.12 1.2615 B.191 C.121.2616 B.192 C.12 1.2617 B.193 C.12 1.2618 B.194 C.12 1.2619 B.195 C.121.2620 B.196 C.12 1.2621 B.197 C.12 1.2622 B.198 C.12 1.2623 B.199 C.121.2624 B.200 C.12 1.2625 B.201 C.12 1.2626 B.202 C.12 1.2627 B.1 C.131.2628 B.2 C.13 1.2629 B.3 C.13 1.2630 B.4 C.13 1.2631 B.5 C.13 1.2632B.6 C.13 1.2633 B.7 C.13 1.2634 B.8 C.13 1.2635 B.9 C.13 1.2636 B.10C.13 1.2637 B.11 C.13 1.2638 B.12 C.13 1.2639 B.13 C.13 1.2640 B.14 C.131.2641 B.15 C.13 1.2642 B.16 C.13 1.2643 B.17 C.13 1.2644 B.18 C.131.2645 B.19 C.13 1.2646 B.20 C.13 1.2647 B.21 C.13 1.2648 B.22 C.131.2649 B.23 C.13 1.2650 B.24 C.13 1.2651 B.25 C.13 1.2652 B.26 C.131.2653 B.27 C.13 1.2654 B.28 C.13 1.2655 B.29 C.13 1.2656 B.30 C.131.2657 B.31 C.13 1.2658 B.32 C.13 1.2659 B.33 C.13 1.2660 B.34 C.131.2661 B.35 C.13 1.2662 B.36 C.13 1.2663 B.37 C.13 1.2664 B.38 C.131.2665 B.39 C.13 1.2666 B.40 C.13 1.2667 B.41 C.13 1.2668 B.42 C.131.2669 B.43 C.13 1.2670 B.44 C.13 1.2671 B.45 C.13 1.2672 B.46 C.131.2673 B.47 C.13 1.2674 B.48 C.13 1.2675 B.49 C.13 1.2676 B.50 C.131.2677 B.51 C.13 1.2678 B.52 C.13 1.2679 B.53 C.13 1.2680 B.54 C.131.2681 B.55 C.13 1.2682 B.56 C.13 1.2683 B.57 C.13 1.2684 B.58. C.131.2685 B.59 C.13 1.2686 B.60 C.13 1.2687 B.61 C.13 1.2688 B.62 C.131.2689 B.63 C.13 1.2690 B.64 C.13 1.2691 B.65 C.13 1.2692 B.66 C.131.2693 B.67 C.13 1.2694 B.68 C.13 1.2695 B.69 C.13 1.2696 B.70 C.131.2697 B.71 C.13 1.2698 B.72 C.13 1.2699 B.73 C.13 1.2700 B.74 C.131.2701 B.75 C.13 1.2702 B.76 C.13 1.2703 B.77 C.13 1.2704 B.78 C.131.2705 B.79 C.13 1.2706 B.80 C.13 1.2707 B.81 C.13 1.2708 B.82 C.131.2709 B.83 C.13 1.2710 B.84 C.13 1.2711 B.85 C.13 1.2712 B.86 C.131.2713 B.87 C.13 1.2714 B.88 C.13 1.2715 B.89 C.13 1.2716 B.90 C.131.2717 B.91 C.13 1.2718 B.92 C.13 1.2719 B.93 C.13 1.2720 B.94 C.131.2721 B.95 C.13 1.2722 B.96 C.13 1.2723 B.97 C.13 1.2724 B.98 C.131.2725 B.99 C.13 1.2726 B.100 C.13 1.2727 B.101 C.13 1.2728 B.102 C.131.2729 B.103 C.13 1.2730 B.104 C.13 1.2731 B.105 C.13 1.2732 B.106 C.131.2733 B.107 C.13 1.2734 B.108 C.13 1.2735 B.109 C.13 1.2736 B.110 C.131.2737 B.111 C.13 1.2738 B.112 C.13 1.2739 B.113 C.13 1.2740 B.114 C.131.2741 B.115 C.13 1.2742 B.116 C.13 1.2743 B.117 C.13 1.2744 B.118 C.131.2745 B.119 C.13 1.2746 B.120 C.13 1.2747 B.121 C.13 1.2748 B.122 C.131.2749 B.123 C.13 1.2750 B.124 C.13 1.2751 B.125 C.13 1.2752 B.126 C.131.2753 B.127 C.13 1.2754 B.128 C.13 1.2755 B.129 C.13 1.2756 B.130 C.131.2757 B.131 C.13 1.2758 B.132 C.13 1.2759 B.133 C.13 1.2760 B.134 C.131.2761 B.135 C.13 1.2762 B.136 C.13 1.2763 B.137 C.13 1.2764 B.138 C.131.2765 B.139 C.13 1.2766 B.140 C.13 1.2767 B.141 C.13 1.2768 B.142 C.131.2769 B.143 C.13 1.2770 B.144 C.13 1.2771 B.145 C.13 1.2772 B.146 C.131.2773 B.147 C.13 1.2774 B.148 C.13 1.2775 B.149 C.13 1.2776 B.150 C.131.2777 B.151 C.13 1.2778 B.152 C.13 1.2779 B.153 C.13 1.2780 B.154 C.131.2781 B.155 C.13 1.2782 B.156 C.13 1.2783 B.157 C.13 1.2784 B.158 C.131.2785 B.159 C.13 1.2786 B.160 C.13 1.2787 B.161 C.13 1.2788 B.162 C.131.2789 B.163 C.13 1.2790 B.164 C.13 1.2791 B.165 C.13 1.2792 B.166 C.131.2793 B.167 C.13 1.2794 B.168 C.13 1.2795 B.169 C.13 1.2796 B.170 C.131.2797 B.171 C.13 1.2798 B.172 C.13 1.2799 B.173 C.13 1.2800 B.174 C.131.2801 B.175 C.13 1.2802 B.176 C.13 1.2803 B.177 C.13 1.2804 B.178 C.131.2805 B.179 C.13 1.2806 B.180 C.13 1.2807 B.181 C.13 1.2808 B.182 C.131.2809 B.183 C.13 1.2810 B.184 C.13 1.2811 B.185 C.13 1.2812 B.186 C.131.2813 B.187 C.13 1.2814 B.188 C.13 1.2815 B.189 C.13 1.2816 B.190 C.131.2817 B.191 C.13 1.2818 B.192 C.13 1.2819 B.193 C.13 1.2820 B.194 C.131.2821 B.195 C.13 1.2822 B.196 C.13 1.2823 B.197 C.13 1.2824 B.198 C.131.2825 B.199 C.13 1.2826 B.200 C.13 1.2827 B.201 C.13 1.2828 B.202 C.131.2829 B.1 C.14 1.2830 B.2 C.14 1.2831 B.3 C.14 1.2832 B.4 C.14 1.2833B.5 C.14 1.2834 B.6 C.14 1.2835 B.7 C.14 1.2836 B.8 C.14 1.2837 B.9 C.141.2838 B.10 C.14 1.2839 B.11 C.14 1.2840 B.12 C.14 1.2841 B.13 C.141.2842 B.14 C.14 1.2843 B.15 C.14 1.2844 B.16 C.14 1.2845 B.17 C.141.2846 B.18 C.14 1.2847 B.19 C.14 1.2848 B.20 C.14 1.2849 B.21 C.141.2850 B.22 C.14 1.2851 B.23 C.14 1.2852 B.24 C.14 1.2853 B.25 C.141.2854 B.26 C.14 1.2855 B.27 C.14 1.2856 B.28 C.14 1.2857 B.29 C.141.2858 B.30 C.14 1.2859 B.31 C.14 1.2860 B.32 C.14 1.2861 B.33 C.141.2862 B.34 C.14 1.2863 B.35 C.14 1.2864 B.36 C.14 1.2865 B.37 C.141.2866 B.38 C.14 1.2867 B.39 C.14 1.2868 B.40 C.14 1.2869 B.41 C.141.2870 B.42 C.14 1.2871 B.43 C.14 1.2872 B.44 C.14 1.2873 B.45 C.141.2874 B.46 C.14 1.2875 B.47 C.14 1.2876 B.48 C.14 1.2877 B.49 C.141.2878 B.50 C.14 1.2879 B.51 C.14 1.2880 B.52 C.14 1.2881 B.53 C.141.2882 B.54 C.14 1.2883 B.55 C.14 1.2884 B.56 C.14 1.2885 B.57 C.141.2886 B.58. C.14 1.2887 B.59 C.14 1.2888 B.60 C.14 1.2889 B.61 C.141.2890 B.62 C.14 1.2891 B.63 C.14 1.2892 B.64 C.14 1.2893 B.65 C.141.2894 B.66 C.14 1.2895 B.67 C.14 1.2896 B.68 C.14 1.2897 B.69 C.141.2898 B.70 C.14 1.2899 B.71 C.14 1.2900 B.72 C.14 1.2901 B.73 C.141.2902 B.74 C.14 1.2903 B.75 C.14 1.2904 B.76 C.14 1.2905 B.77 C.141.2906 B.78 C.14 1.2907 B.79 C.14 1.2908 B.80 C.14 1.2909 B.81 C.141.2910 B.82 C.14 1.2911 B.83 C.14 1.2912 B.84 C.14 1.2913 B.85 C.141.2914 B.86 C.14 1.2915 B.87 C.14 1.2916 B.88 C.14 1.2917 B.89 C.141.2918 B.90 C.14 1.2919 B.91 C.14 1.2920 B.92 C.14 1.2921 B.93 C.141.2922 B.94 C.14 1.2923 B.95 C.14 1.2924 B.96 C.14 1.2925 B.97 C.141.2926 B.98 C.14 1.2927 B.99 C.14 1.2928 B.100 C.14 1.2929 B.101 C.141.2930 B.102 C.14 1.2931 B.103 C.14 1.2932 B.104 C.14 1.2933 B.105 C.141.2934 B.106 C.14 1.2935 B.107 C.14 1.2936 B.108 C.14 1.2937 B.109 C.141.2938 B.110 C.14 1.2939 B.111 C.14 1.2940 B.112 C.14 1.2941 B.113 C.141.2942 B.114 C.14 1.2943 B.115 C.14 1.2944 B.116 C.14 1.2945 B.117 C.141.2946 B.118 C.14 1.2947 B.119 C.14 1.2948 B.120 C.14 1.2949 B.121 C.141.2950 B.122 C.14 1.2951 B.123 C.14 1.2952 B.124 C.14 1.2953 B.125 C.141.2954 B.126 C.14 1.2955 B.127 C.14 1.2956 B.128 C.14 1.2957 B.129 C.141.2958 B.130 C.14 1.2959 B.131 C.14 1.2960 B.132 C.14 1.2961 B.133 C.141.2962 B.134 C.14 1.2963 B.135 C.14 1.2964 B.136 C.14 1.2965 B.137 C.141.2966 B.138 C.14 1.2967 B.139 C.14 1.2968 B.140 C.14 1.2969 B.141 C.141.2970 B.142 C.14 1.2971 B.143 C.14 1.2972 B.144 C.14 1.2973 B.145 C.141.2974 B.146 C.14 1.2975 B.147 C.14 1.2976 B.148 C.14 1.2977 B.149 C.141.2978 B.150 C.14 1.2979 B.151 C.14 1.2980 B.152 C.14 1.2981 B.153 C.141.2982 B.154 C.14 1.2983 B.155 C.14 1.2984 B.156 C.14 1.2985 B.157 C.141.2986 B.158 C.14 1.2987 B.159 C.14 1.2988 B.160 C.14 1.2989 B.161 C.141.2990 B.162 C.14 1.2991 B.163 C.14 1.2992 B.164 C.14 1.2993 B.165 C.141.2994 B.166 C.14 1.2995 B.167 C.14 1.2996 B.168 C.14 1.2997 B.169 C.141.2998 B.170 C.14 1.2999 B.171 C.14 1.3000 B.172 C.14 1.3001 B.173 C.141.3002 B.174 C.14 1.3003 B.175 C.14 1.3004 B.176 C.14 1.3005 B.177 C.141.3006 B.178 C.14 1.3007 B.179 C.14 1.3008 B.180 C.14 1.3009 B.181 C.141.3010 B.182 C.14 1.3011 B.183 C.14 1.3012 B.184 C.14 1.3013 B.185 C.141.3014 B.186 C.14 1.3015 B.187 C.14 1.3016 B.188 C.14 1.3017 B.189 C.141.3018 B.190 C.14 1.3019 B.191 C.14 1.3020 B.192 C.14 1.3021 B.193 C.141.3022 B.194 C.14 1.3023 B.195 C.14 1.3024 B.196 C.14 1.3025 B.197 C.141.3026 B.198 C.14 1.3027 B.199 C.14 1.3028 B.200 C.14 1.3029 B.201 C.141.3030 B.202 C.14 1.3031 B.1 C.15 1.3032 B.2 C.15 1.3033 B.3 C.15 1.3034B.4 C.15 1.3035 B.5 C.15 1.3036 B.6 C.15 1.3037 B.7 C.15 1.3038 B.8 C.151.3039 B.9 C.15 1.3040 B.10 C.15 1.3041 B.11 C.15 1.3042 B.12 C.151.3043 B.13 C.15 1.3044 B.14 C.15 1.3045 B.15 C.15 1.3046 B.16 C.151.3047 B.17 C.15 1.3048 B.18 C.15 1.3049 B.19 C.15 1.3050 B.20 C.151.3051 B.21 C.15 1.3052 B.22 C.15 1.3053 B.23 C.15 1.3054 B.24 C.151.3055 B.25 C.15 1.3056 B.26 C.15 1.3057 B.27 C.15 1.3058 B.28 C.151.3059 B.29 C.15 1.3060 B.30 C.15 1.3061 B.31 C.15 1.3062 B.32 C.151.3063 B.33 C.15 1.3064 B.34 C.15 1.3065 B.35 C.15 1.3066 B.36 C.151.3067 B.37 C.15 1.3068 B.38 C.15 1.3069 B.39 C.15 1.3070 B.40 C.151.3071 B.41 C.15 1.3072 B.42 C.15 1.3073 B.43 C.15 1.3074 B.44 C.151.3075 B.45 C.15 1.3076 B.46 C.15 1.3077 B.47 C.15 1.3078 B.48 C.151.3079 B.49 C.15 1.3080 B.50 C.15 1.3081 B.51 C.15 1.3082 B.52 C.151.3083 B.53 C.15 1.3084 B.54 C.15 1.3085 B.55 C.15 1.3086 B.56 C.151.3087 B.57 C.15 1.3088 B.58. C.15 1.3089 B.59 C.15 1.3090 B.60 C.151.3091 B.61 C.15 1.3092 B.62 C.15 1.3093 B.63 C.15 1.3094 B.64 C.151.3095 B.65 C.15 1.3096 B.66 C.15 1.3097 B.67 C.15 1.3098 B.68 C.151.3099 B.69 C.15 1.3100 B.70 C.15 1.3101 B.71 C.15 1.3102 B.72 C.151.3103 B.73 C.15 1.3104 B.74 C.15 1.3105 B.75 C.15 1.3106 B.76 C.151.3107 B.77 C.15 1.3108 B.78 C.15 1.3109 B.79 C.15 1.3110 B.80 C.151.3111 B.81 C.15 1.3112 B.82 C.15 1.3113 B.83 C.15 1.3114 B.84 C.151.3115 B.85 C.15 1.3116 B.86 C.15 1.3117 B.87 C.15 1.3118 B.88 C.151.3119 B.89 C.15 1.3120 B.90 C.15 1.3121 B.91 C.15 1.3122 B.92 C.151.3123 B.93 C.15 1.3124 B.94 C.15 1.3125 B.95 C.15 1.3126 B.96 C.151.3127 B.97 C.15 1.3128 B.98 C.15 1.3129 B.99 C.15 1.3130 B.100 C.151.3131 B.101 C.15 1.3132 B.102 C.15 1.3133 B.103 C.15 1.3134 B.104 C.151.3135 B.105 C.15 1.3136 B.106 C.15 1.3137 B.107 C.15 1.3138 B.108 C.151.3139 B.109 C.15 1.3140 B.110 C.15 1.3141 B.111 C.15 1.3142 B.112 C.151.3143 B.113 C.15 1.3144 B.114 C.15 1.3145 B.115 C.15 1.3146 B.116 C.151.3147 B.117 C.15 1.3148 B.118 C.15 1.3149 B.119 C.15 1.3150 B.120 C.151.3151 B.121 C.15 1.3152 B.122 C.15 1.3153 B.123 C.15 1.3154 B.124 C.151.3155 B.125 C.15 1.3156 B.126 C.15 1.3157 B.127 C.15 1.3158 B.128 C.151.3159 B.129 C.15 1.3160 B.130 C.15 1.3161 B.131 C.15 1.3162 B.132 C.151.3163 B.133 C.15 1.3164 B.134 C.15 1.3165 B.135 C.15 1.3166 B.136 C.151.3167 B.137 C.15 1.3168 B.138 C.15 1.3169 B.139 C.15 1.3170 B.140 C.151.3171 B.141 C.15 1.3172 B.142 C.15 1.3173 B.143 C.15 1.3174 B.144 C.151.3175 B.145 C.15 1.3176 B.146 C.15 1.3177 B.147 C.15 1.3178 B.148 C.151.3179 B.149 C.15 1.3180 B.150 C.15 1.3181 B.151 C.15 1.3182 B.152 C.151.3183 B.153 C.15 1.3184 B.154 C.15 1.3185 B.155 C.15 1.3186 B.156 C.151.3187 B.157 C.15 1.3188 B.158 C.15 1.3189 B.159 C.15 1.3190 B.160 C.151.3191 B.161 C.15 1.3192 B.162 C.15 1.3193 B.163 C.15 1.3194 B.164 C.151.3195 B.165 C.15 1.3196 B.166 C.15 1.3197 B.167 C.15 1.3198 B.168 C.151.3199 B.169 C.15 1.3200 B.170 C.15 1.3201 B.171 C.15 1.3202 B.172 C.151.3203 B.173 C.15 1.3204 B.174 C.15 1.3205 B.175 C.15 1.3206 B.176 C.151.3207 B.177 C.15 1.3208 B.178 C.15 1.3209 B.179 C.15 1.3210 B.180 C.151.3211 B.181 C.15 1.3212 B.182 C.15 1.3213 B.183 C.15 1.3214 B.184 C.151.3215 B.185 C.15 1.3216 B.186 C.15 1.3217 B.187 C.15 1.3218 B.188 C.151.3219 B.189 C.15 1.3220 B.190 C.15 1.3221 B.191 C.15 1.3222 B.192 C.151.3223 B.193 C.15 1.3224 B.194 C.15 1.3225 B.195 C.15 1.3226 B.196 C.151.3227 B.197 C.15 1.3228 B.198 C.15 1.3229 B.199 C.15 1.3230 B.200 C.151.3231 B.201 C.15 1.3232 B.202 C.15 1.3233 B.1 C.16 1.3234 B.2 C.161.3235 B.3 C.16 1.3236 B.4 C.16 1.3237 B.5 C.16 1.3238 B.6 C.16 1.3239B.7 C.16 1.3240 B.8 C.16 1.3241 B.9 C.16 1.3242 B.10 C.16 1.3243 B.11C.16 1.3244 B.12 C.16 1.3245 B.13 C.16 1.3246 B.14 C.16 1.3247 B.15 C.161.3248 B.16 C.16 1.3249 B.17 C.16 1.3250 B.18 C.16 1.3251 B.19 C.161.3252 B.20 C.16 1.3253 B.21 C.16 1.3254 B.22 C.16 1.3255 B.23 C.161.3256 B.24 C.16 1.3257 B.25 C.16 1.3258 B.26 C.16 1.3259 B.27 C.161.3260 B.28 C.16 1.3261 B.29 C.16 1.3262 B.30 C.16 1.3263 B.31 C.161.3264 B.32 C.16 1.3265 B.33 C.16 1.3266 B.34 C.16 1.3267 B.35 C.161.3268 B.36 C.16 1.3269 B.37 C.16 1.3270 B.38 C.16 1.3271 B.39 C.161.3272 B.40 C.16 1.3273 B.41 C.16 1.3274 B.42 C.16 1.3275 B.43 C.161.3276 B.44 C.16 1.3277 B.45 C.16 1.3278 B.46 C.16 1.3279 B.47 C.161.3280 B.48 C.16 1.3281 B.49 C.16 1.3282 B.50 C.16 1.3283 B.51 C.161.3284 B.52 C.16 1.3285 B.53 C.16 1.3286 B.54 C.16 1.3287 B.55 C.161.3288 B.56 C.16 1.3289 B.57 C.16 1.3290 B.58. C.16 1.3291 B.59 C.161.3292 B.60 C.16 1.3293 B.61 C.16 1.3294 B.62 C.16 1.3295 B.63 C.161.3296 B.64 C.16 1.3297 B.65 C.16 1.3298 B.66 C.16 1.3299 B.67 C.161.3300 B.68 C.16 1.3301 B.69 C.16 1.3302 B.70 C.16 1.3303 B.71 C.161.3304 B.72 C.16 1.3305 B.73 C.16 1.3306 B.74 C.16 1.3307 B.75 C.161.3308 B.76 C.16 1.3309 B.77 C.16 1.3310 B.78 C.16 1.3311 B.79 C.161.3312 B.80 C.16 1.3313 B.81 C.16 1.3314 B.82 C.16 1.3315 B.83 C.161.3316 B.84 C.16 1.3317 B.85 C.16 1.3318 B.86 C.16 1.3319 B.87 C.161.3320 B.88 C.16 1.3321 B.89 C.16 1.3322 B.90 C.16 1.3323 B.91 C.161.3324 B.92 C.16 1.3325 B.93 C.16 1.3326 B.94 C.16 1.3327 B.95 C.161.3328 B.96 C.16 1.3329 B.97 C.16 1.3330 B.98 C.16 1.3331 B.99 C.161.3332 B.100 C.16 1.3333 B.101 C.16 1.3334 B.102 C.16 1.3335 B.103 C.161.3336 B.104 C.16 1.3337 B.105 C.16 1.3338 B.106 C.16 1.3339 B.107 C.161.3340 B.108 C.16 1.3341 B.109 C.16 1.3342 B.110 C.16 1.3343 B.111 C.161.3344 B.112 C.16 1.3345 B.113 C.16 1.3346 B.114 C.16 1.3347 B.115 C.161.3348 B.116 C.16 1.3349 B.117 C.16 1.3350 B.118 C.16 1.3351 B.119 C.161.3352 B.120 C.16 1.3353 B.121 C.16 1.3354 B.122 C.16 1.3355 B.123 C.161.3356 B.124 C.16 1.3357 B.125 C.16 1.3358 B.126 C.16 1.3359 B.127 C.161.3360 B.128 C.16 1.3361 B.129 C.16 1.3362 B.130 C.16 1.3363 B.131 C.161.3364 B.132 C.16 1.3365 B.133 C.16 1.3366 B.134 C.16 1.3367 B.135 C.161.3368 B.136 C.16 1.3369 B.137 C.16 1.3370 B.138 C.16 1.3371 B.139 C.161.3372 B.140 C.16 1.3373 B.141 C.16 1.3374 B.142 C.16 1.3375 B.143 C.161.3376 B.144 C.16 1.3377 B.145 C.16 1.3378 B.146 C.16 1.3379 B.147 C.161.3380 B.148 C.16 1.3381 B.149 C.16 1.3382 B.150 C.16 1.3383 B.151 C.161.3384 B.152 C.16 1.3385 B.153 C.16 1.3386 B.154 C.16 1.3387 B.155 C.161.3388 B.156 C.16 1.3389 B.157 C.16 1.3390 B.158 C.16 1.3391 B.159 C.161.3392 B.160 C.16 1.3393 B.161 C.16 1.3394 B.162 C.16 1.3395 B.163 C.161.3396 B.164 C.16 1.3397 B.165 C.16 1.3398 B.166 C.16 1.3399 B.167 C.161.3400 B.168 C.16 1.3401 B.169 C.16 1.3402 B.170 C.16 1.3403 B.171 C.161.3404 B.172 C.16 1.3405 B.173 C.16 1.3406 B.174 C.16 1.3407 B.175 C.161.3408 B.176 C.16 1.3409 B.177 C.16 1.3410 B.178 C.16 1.3411 B.179 C.161.3412 B.180 C.16 1.3413 B.181 C.16 1.3414 B.182 C.16 1.3415 B.183 C.161.3416 B.184 C.16 1.3417 B.185 C.16 1.3418 B.186 C.16 1.3419 B.187 C.161.3420 B.188 C.16 1.3421 B.189 C.16 1.3422 B.190 C.16 1.3423 B.191 C.161.3424 B.192 C.16 1.3425 B.193 C.16 1.3426 B.194 C.16 1.3427 B.195 C.161.3428 B.196 C.16 1.3429 B.197 C.16 1.3430 B.198 C.16 1.3431 B.199 C.161.3432 B.200 C.16 1.3433 B.201 C.16 1.3434 B.202 C.16 1.3435 B.1 C.171.3436 B.2 C.17 1.3437 B.3 C.17 1.3438 B.4 C.17 1.3439 B.5 C.17 1.3440B.6 C.17 1.3441 B.7 C.17 1.3442 B.8 C.17 1.3443 B.9 C.17 1.3444 B.10C.17 1.3445 B.11 C.17 1.3446 B.12 C.17 1.3447 B.13 C.17 1.3448 B.14 C.171.3449 B.15 C.17 1.3450 B.16 C.17 1.3451 B.17 C.17 1.3452 B.18 C.171.3453 B.19 C.17 1.3454 B.20 C.17 1.3455 B.21 C.17 1.3456 B.22 C.171.3457 B.23 C.17 1.3458 B.24 C.17 1.3459 B.25 C.17 1.3460 B.26 C.171.3461 B.27 C.17 1.3462 B.28 C.17 1.3463 B.29 C.17 1.3464 B.30 C.171.3465 B.31 C.17 1.3466 B.32 C.17 1.3467 B.33 C.17 1.3468 B.34 C.171.3469 B.35 C.17 1.3470 B.36 C.17 1.3471 B.37 C.17 1.3472 B.38 C.171.3473 B.39 C.17 1.3474 B.40 C.17 1.3475 B.41 C.17 1.3476 B.42 C.171.3477 B.43 C.17 1.3478 B.44 C.17 1.3479 B.45 C.17 1.3480 B.46 C.171.3481 B.47 C.17 1.3482 B.48 C.17 1.3483 B.49 C.17 1.3484 B.50 C.171.3485 B.51 C.17 1.3486 B.52 C.17 1.3487 B.53 C.17 1.3488 B.54 C.171.3489 B.55 C.17 1.3490 B.56 C.17 1.3491 B.57 C.17 1.3492 B.58. C.171.3493 B.59 C.17 1.3494 B.60 C.17 1.3495 B.61 C.17 1.3496 B.62 C.171.3497 B.63 C.17 1.3498 B.64 C.17 1.3499 B.65 C.17 1.3500 B.66 C.171.3501 B.67 C.17 1.3502 B.68 C.17 1.3503 B.69 C.17 1.3504 B.70 C.171.3505 B.71 C.17 1.3506 B.72 C.17 1.3507 B.73 C.17 1.3508 B.74 C.171.3509 B.75 C.17 1.3510 B.76 C.17 1.3511 B.77 C.17 1.3512 B.78 C.171.3513 B.79 C.17 1.3514 B.80 C.17 1.3515 B.81 C.17 1.3516 B.82 C.171.3517 B.83 C.17 1.3518 B.84 C.17 1.3519 B.85 C.17 1.3520 B.86 C.171.3521 B.87 C.17 1.3522 B.88 C.17 1.3523 B.89 C.17 1.3524 B.90 C.171.3525 B.91 C.17 1.3526 B.92 C.17 1.3527 B.93 C.17 1.3528 B.94 C.171.3529 B.95 C.17 1.3530 B.96 C.17 1.3531 B.97 C.17 1.3532 B.98 C.171.3533 B.99 C.17 1.3534 B.100 C.17 1.3535 B.101 C.17 1.3536 B.102 C.171.3537 B.103 C.17 1.3538 B.104 C.17 1.3539 B.105 C.17 1.3540 B.106 C.171.3541 B.107 C.17 1.3542 B.108 C.17 1.3543 B.109 C.17 1.3544 B.110 C.171.3545 B.111 C.17 1.3546 B.112 C.17 1.3547 B.113 C.17 1.3548 B.114 C.171.3549 B.115 C.17 1.3550 B.116 C.17 1.3551 B.117 C.17 1.3552 B.118 C.171.3553 B.119 C.17 1.3554 B.120 C.17 1.3555 B.121 C.17 1.3556 B.122 C.171.3557 B.123 C.17 1.3558 B.124 C.17 1.3559 B.125 C.17 1.3560 B.126 C.171.3561 B.127 C.17 1.3562 B.128 C.17 1.3563 B.129 C.17 1.3564 B.130 C.171.3565 B.131 C.17 1.3566 B.132 C.17 1.3567 B.133 C.17 1.3568 B.134 C.171.3569 B.135 C.17 1.3570 B.136 C.17 1.3571 B.137 C.17 1.3572 B.138 C.171.3573 B.139 C.17 1.3574 B.140 C.17 1.3575 B.141 C.17 1.3576 B.142 C.171.3577 B.143 C.17 1.3578 B.144 C.17 1.3579 B.145 C.17 1.3580 B.146 C.171.3581 B.147 C.17 1.3582 B.148 C.17 1.3583 B.149 C.17 1.3584 B.150 C.171.3585 B.151 C.17 1.3586 B.152 C.17 1.3587 B.153 C.17 1.3588 B.154 C.171.3589 B.155 C.17 1.3590 B.156 C.17 1.3591 B.157 C.17 1.3592 B.158 C.171.3593 B.159 C.17 1.3594 B.160 C.17 1.3595 B.161 C.17 1.3596 B.162 C.171.3597 B.163 C.17 1.3598 B.164 C.17 1.3599 B.165 C.17 1.3600 B.166 C.171.3601 B.167 C.17 1.3602 B.168 C.17 1.3603 B.169 C.17 1.3604 B.170 C.171.3605 B.171 C.17 1.3606 B.172 C.17 1.3607 B.173 C.17 1.3608 B.174 C.171.3609 B.175 C.17 1.3610 B.176 C.17 1.3611 B.177 C.17 1.3612 B.178 C.171.3613 B.179 C.17 1.3614 B.180 C.17 1.3615 B.181 C.17 1.3616 B.182 C.171.3617 B.183 C.17 1.3618 B.184 C.17 1.3619 B.185 C.17 1.3620 B.186 C.171.3621 B.187 C.17 1.3622 B.188 C.17 1.3623 B.189 C.17 1.3624 B.190 C.171.3625 B.191 C.17 1.3626 B.192 C.17 1.3627 B.193 C.17 1.3628 B.194 C.171.3629 B.195 C.17 1.3630 B.196 C.17 1.3631 B.197 C.17 1.3632 B.198 C.171.3633 B.199 C.17 1.3634 B.200 C.17 1.3635 B.201 C.17 1.3636 B.202 C.171.3637 — C.1 1.3638 — C.2 1.3639 — C.3 1.3640 — C.4 1.3641 — C.5 1.3642— C.6 1.3643 — C.7 1.3644 — C.8 1.3645 — C.9 1.3646 — C.10 1.3647 — C.111.3648 — C.12 1.3649 — C.13 1.3650 — C.14 1.3651 — C.15 1.3652 — C.161.3653 — C.17

The specific number for each single composition is deductible asfollows:

Composition 1.300 for example comprises form C of the compound offormula (I), benzobicyclon (B.98) and benoxacor (C.1) (see table 1,entry 1.300; as well as table B, entry B.98 and table C, entry C.1).

Composition 2.300 for example comprises form A of the compound offormula (I) (see the definition for compositions 2.1 to 2.3653 below),benzobicyclon (B.98) and benoxacor (C.1) (see table 1, entry 1.300; aswell as table B, entry B.98 and table C, entry C.1).

Composition 7.300 for example comprises imazapyr (B.35) (see thedefinition for compositions 7.1 to 7.3653 below), and form C of thecompound of formula (I), benzobicyclon (B.98) and benoxacor (C.1) (seetable 1, entry 1.300; as well as table B, entry B.98 and table C, entryC.1).

Also especially preferred are compositions 2.1. to 2.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theycomprise form A as the active component A.

Also especially preferred are compositions 3.1. to 3.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.2 as further herbicide B.

Also especially preferred are compositions 4.1. to 4.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.8 as further herbicide B.

Also especially preferred are compositions 5.1. to 5.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.30 as further herbicide B.

Also especially preferred are compositions 6.1. to 6.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.32 as further herbicide B.

Also especially preferred are compositions 7.1. to 7.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.35 as further herbicide B.

Also especially preferred are compositions 8.1. to 8.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.38 as further herbicide B.

Also especially preferred are compositions 9.1. to 9.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.40 as further herbicide B.

Also especially preferred are compositions 10.1. to 10.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.51 as further herbicide B.

Also especially preferred are compositions 11.1. to 11.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.55 as further herbicide B.

Also especially preferred are compositions 12.1. to 12.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.56 as further herbicide B.

Also especially preferred are compositions 13.1. to 13.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.64 as further herbicide B.

Also especially preferred are compositions 14.1. to 14.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.66 as further herbicide B.

Also especially preferred are compositions 15.1. to 15.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.67 as further herbicide B.

Also especially preferred are compositions 16.1. to 16.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.68 as further herbicide B.

Also especially preferred are compositions 17.1. to 17.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.69 as further herbicide B.

Also especially preferred are compositions 18.1. to 18.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.73 as further herbicide B.

Also especially preferred are compositions 19.1. to 19.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.76 as further herbicide B.

Also especially preferred are compositions 20.1. to 20.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.81 as further herbicide B.

Also especially preferred are compositions 21.1. to 21.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.82 as further herbicide B.

Also especially preferred are compositions 22.1. to 22.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.85 as further herbicide B.

Also especially preferred are compositions 23.1. to 23.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.88 as further herbicide B.

Also especially preferred are compositions 24.1. to 24.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.89 as further herbicide B.

Also especially preferred are compositions 25.1. to 25.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.94 as further herbicide B.

Also especially preferred are compositions 26.1. to 26.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.95 as further herbicide B.

Also especially preferred are compositions 27.1. to 27.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.98 as further herbicide B.

Also especially preferred are compositions 28.1. to 28.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.100 as further herbicide B.

Also especially preferred are compositions 29.1. to 29.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.103 as further herbicide B.

Also especially preferred are compositions 30.1. to 30.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.103 and B.67 as further herbicides B.

Also especially preferred are compositions 31.1. to 31.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.103 and B.76 as further herbicides B.

Also especially preferred are compositions 32.1. to 32.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.103 and B.82 as further herbicides B.

Also especially preferred are compositions 33.1. to 33.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.104 as further herbicide B.

Also especially preferred are compositions 34.1. to 34.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.104 and B.67 as further herbicides B.

Also especially preferred are compositions 35.1. to 35.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.104 and B.76/as further herbicides B.

Also especially preferred are compositions 36.1. to 36.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.104 and B.82 as further herbicides B.

Also especially preferred are compositions 37.1. to 37.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.106 as further herbicide B.

Also especially preferred are compositions 38.1. to 38.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.107 as further herbicide B.

Also especially preferred are compositions 39.1. to 39.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B. 107 and B.67 as further herbicides B.

Also especially preferred are compositions 40.1. to 40.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B. 107 and B.76 as further herbicides B.

Also especially preferred are compositions 41.1. to 41.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B. 107 and B.82 as further herbicides B.

Also especially preferred are compositions 42.1. to 42.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.109 as further herbicide B.

Also especially preferred are compositions 43.1. to 43.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.111 as further herbicide B.

Also especially preferred are compositions 44.1. to 44.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.111 and B.67 as further herbicides B.

Also especially preferred are compositions 45.1. to 45.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.111 and B.76 as further herbicides B.

Also especially preferred are compositions 46.1. to 46.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.111 and B.82 as further herbicides B.

Also especially preferred are compositions 47.1. to 47.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B. 116 as further herbicide B.

Also especially preferred are compositions 48.1. to 48.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.67 as further herbicides B.

Also especially preferred are compositions 49.1. to 49.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.94 as further herbicides B.

Also especially preferred are compositions 50.1. to 50.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.103 as further herbicides B.

Also especially preferred are compositions 51.1. to 51.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.128 as further herbicides B.

Also especially preferred are compositions 52.1. to 52.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.104 as further herbicides B.

Also especially preferred are compositions 53.1. to 53.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.107 as further herbicides B.

Also especially preferred are compositions 54.1. to 54.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.116 and B.111 as further herbicides B.

Also especially preferred are compositions 55.1. to 55.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.122 as further herbicide B.

Also especially preferred are compositions 56.1. to 56.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.126 as further herbicide B.

Also especially preferred are compositions 57.1. to 57.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.128 as further herbicide B.

Also especially preferred are compositions 58.1. to 58.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.131 as further herbicide B.

Also especially preferred are compositions 59.1. to 59.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.132 as further herbicide B.

Also especially preferred are compositions 60.1. to 60.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.133 as further herbicide B.

Also especially preferred are compositions 61.1. to 61.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.135 as further herbicide B.

Also especially preferred are compositions 62.1. to 62.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.137 as further herbicide B.

Also especially preferred are compositions 63.1. to 63.3653 which differfrom the corresponding compositions 11.1 to 1.3653 only in that theyadditionally comprise B.138 as further herbicide B.

Also especially preferred are compositions 64.1. to 64.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.140 as further herbicide B.

Also especially preferred are compositions 65.1. to 65.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.145 as further herbicide B.

Also especially preferred are compositions 66.1. to 66.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.153 as further herbicide B.

Also especially preferred are compositions 67.1. to 67.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.156 as further herbicide B.

Also especially preferred are compositions 68.1. to 68.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.171 as further herbicide B.

Also especially preferred are compositions 69.1. to 69.3653 which differfrom the corresponding compositions 1.1 to 1.3653 only in that theyadditionally comprise B.174 as further herbicide B.

The invention also relates to agrochemical compositions comprising atleast an auxiliary and at least one compound of formula (I) in the formA, B, C and/or D, preferably form C, according to the invention.

An agrochemical composition comprises a pesticidally effective amount ofa compound of formula (I) in the form A, B, C and/or D, preferably formC. The term “effective amount” denotes an amount of the composition orof the compounds I, which is sufficient for controlling unwanted plants,especially for controlling unwanted plants in crops (i.e. cultivatedplants) and which does not result in a substantial damage to the treatedplants. Such an amount can vary in a broad range and is dependent onvarious factors, such as the plants to be controlled, the treated cropsor material, the climatic conditions and the specific compound offormula (I) in the form A, B, C and/or D, preferably form C, used.

Compound of formula (I) in the form A, B, C and/or D, preferably form C,or the plant protection agents containing them can for example be usedin the form of directly sprayable aqueous solutions, powders,suspensions and also high concentration aqueous, oily or othersuspensions, oil suspensions, pastes, dusting agents, scattering agentsor granules by spraying, misting, dusting, scattering or pouring. Theuse forms are determined by the use purposes; in each case, they shouldensure the finest possible distribution of the active substancesaccording to the invention.

The plant protection agents according to the invention contain compoundof formula (I) either in form A, B, C and/or D, preferably form C, i.e.in a purity, based on the modification in question, of at least 90 wt.%, and additives and/or carriers such as are usual for the formulationof plant protection agents. In such plant protection agents, thequantity of active substance, i.e. the total quantity of compound offormula (I) and of other active substances if necessary, normally liesin the range from 1 to 98 wt. %, in particular in the range from 10 to95 wt. %, based on the total weight of the plant protection agent.

All solid and liquid substances which are normally used as carriers inplant protection agents, in particular in herbicide formulations arepossible as carriers.

The compound of formula (I) in the form A, B, C and/or D, preferablyform C, can be converted into customary types of agrochemicalcompositions, e. g. suspensions, dusts, powders, pastes, granules,pressings, capsules, and mixtures thereof. Examples for agrochemicalcomposition types are suspensions (e.g. SC, OD, FS), capsules (e.g. CS,ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP,DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG,MG), insecticidal articles (e.g. LN), as well as gel formulations forthe treatment of plant propagation materials such as seeds (e.g. GF).These and further agrochemical compositions types are defined in the“Catalogue of pesticide formulation types and international codingsystem”, Technical Monograph No. 2, 6^(th) Ed. May 2008, CropLifeInternational.

The agrochemical compositions are prepared in a known manner, such asdescribed by Mollet and Grubemann, Formulation technology, Wiley VCH,Weinheim, 2001; or Knowles, New developments in crop protection productformulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers orfillers, surfactants, dispersants, emulsifiers, wetters, adjuvants,solubilizers, penetration enhancers, protective colloids, adhesionagents, thickeners, humectants, repellents, attractants, feedingstimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones,e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers,e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas;products of vegetable origin, e.g. cereal meal, tree bark meal, woodmeal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemulsifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acidamides, amine oxides, esters, sugar-based surfactants, polymericsurfactants, and mixtures thereof. Examples of alkoxylates are compoundssuch as alcohols, alkylphenols, amines, amides, arylphenols, fatty acidsor fatty acid esters which have been alkoxylated with 1 to 50equivalents. Ethylene oxide and/or propylene oxide may be employed forthe alkoxylation, preferably ethylene oxide. Examples of N-substitutedfatty acid amides are fatty acid glucamides or fatty acid alkanolamides.Examples of esters are fatty acid esters, glycerol esters ormonoglycerides. Examples of sugar-based surfactants are sorbitans,ethoxylated sorbitans, sucrose and glucose esters oralkylpolyglucosides. Examples of polymeric surfactants are home- orcopolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the compound of formula (I) in the forms A or B on thetarget. Examples are surfactants, mineral or vegetable oils, and otherauxiliaries. Further examples are listed by Knowles, Adjuvants andadditives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), inorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidones,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

If the plant protection agents containing the crystalline modificationform A, B, C and/or D, preferably form C, are used for seed treatment,they can also contain normal components such as are used for seedtreatment, for example in dressing or coating. In addition to theaforesaid components, these include in particular colorants, adhesives,fillers and plasticizers.

All the dyes and pigments usual for such purposes are possible ascolorants. Both pigments of low solubility in water and also dyessoluble in water are usable here. As examples, the dyes and pigmentsknown under the names Rhodamin B, C.I. Pigment Red 112 and C.I. SolventRed 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, PigmentBlue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, PigmentRed 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, PigmentOrange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36,Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10,Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9,Acid Yellow 23, Basic Red 10, Basic Red 10 and Basic Red 108 may bementioned. The quantity of colorant will normally not constitute morethan 20 wt. % of the formulation and preferably lies in the range from0.1 to 15 wt. %, based on the total weight of the formulation.

All binders normally usable in dressings come under consideration asadhesives. Examples of suitable binders include thermoplastic polymerssuch as polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol andtylose and also polyacrylates, polymethacrylates, polybutenes,polyisobutenes, polystyrene, polyethylene amines, polyethylene amides,the aforesaid protective colloids, polyesters, polyether esters,polyanhydrides, polyester urethanes, polyester amides, thermoplasticpolysaccharides, for example cellulose derivatives such as celluloseesters, cellulose ethers, cellulose ether esters, includingmethylcellulose, ethylcellulose, hydroxymethylcellulose,carboxymethylcellulose, hydroxypropyl cellulose and starch derivativesand modified starches, dextrins, maltodextrins, alginates and chitosans,and also fats, oils, proteins, including casein, gelatin and zein, gumArabic and shellac. The adhesives are preferably plant-compatible, i.e.they exhibit no, or no significant, phytotoxic effects. The adhesivesare preferably biodegradable. The adhesive is preferably selected suchthat it acts as a matrix for the active components of the formulation.The quantity of adhesive will normally not constitute more than 40 wt. %of the formulation and preferably lies in the range from 1 to 40 wt. %and in particular in the range from 5 to 30 wt. %, based on the totalweight of the formulation.

In addition to the adhesive, the formulation for seed treatment can alsocontain inert fillers. Examples of these are the aforesaid solidcarriers, in particular finely divided inorganic materials such asclays, chalk, bentonite, kaolin, talc, perlite, mica, silica gel,diatomaceous earth, quartz powder and montmorillonite but alsofine-particle organic materials such as wood flour, cereal flour, activecharcoal and the like. The quantity of filler is preferably selectedsuch that the total quantity of filler does not exceed 70 wt. %, basedon the total weight of all non-volatile components of the formulation.Often, the quantity of filler lies in the range from 1 to 50 wt. %,based on the total weight of all non-volatile components of theformulation.

In addition, the formulation for seed treatment can also contain aplasticizer which increases the flexibility of the coating. Examples ofplasticizers are oligomeric polyalkylene glycols, glycerine, dialkylphthalates, alkylbenzyl phthalates, glycol benzoates and comparablecompounds. The quantity of plasticizer in the coating often lies in therange from 0.1 to 20 wt. %, based on the total weight of allnon-volatile components of the formulation.

A preferred embodiment of the invention relates to liquid formulationsof the form A, B, C and/or D, preferably form C. In addition to thesolid active substance phase, these have at least one liquid phase, inwhich compound of formula (I) is present in form A, B, C and/or D,preferably form C, in the form of dispersed fine particles.

Possible liquid phases are essentially water and those organic solventsin which the form A, B, C and/or D, preferably form C, is only slightlysoluble, or insoluble, for example those wherein the solubility of theform A or form B at 25° C. and 1013 mbar is not more than 1 wt. %, inparticular not more than 0.1 wt. %, and especially not more than 0.01wt. %.

According to a first preferred embodiment, the liquid phase is selectedfrom water and aqueous solvents, i.e. solvent mixtures which in additionto water also contain up to 20 wt. %, preferably however not more than10 wt. %, based on the total quantity of water and solvent, of one ormore organic solvents miscible with water, for example ethers misciblewith water such as tetrahydrofuran, methyl glycol, methyl diglycol,alkanols such as isopropanol or polyols such as glycol, glycerine,diethylene glycol, propylene glycol and the like. Such formulations arealso referred to below as suspension concentrates (SCs).

Such suspension concentrates contain compound of formula (I) as form A,B, C and/or D, preferably form C, in a finely divided particulate form,wherein the particles of the form A, B, C and/or D, preferably form C,are present suspended in an aqueous phase. The size of the activesubstance particles, i.e. the size which 90 wt. % of the activesubstance particles do not exceed, here typically lies below 30 μm, inparticular below 20 μm. Advantageously, in the SCs according to theinvention, at least 40 wt. % and in particular at least 60 wt. % of theparticles have diameters below 2 μm.

In such SCs the quantity of active substance, i.e. the total quantity ofcompound of formula (I) and of other active substances if necessary,usually lies in the range from 5 to 70 wt. %, in particular in the rangefrom 10 to 50 wt. %, based on the total weight of the suspensionconcentrate.

In addition to the active substance, aqueous suspension concentratestypically contain surface-active substances, and also if necessaryantifoaming agents, thickeners (=rheology modifiers), antifreeze agents,stabilizers (biocides), agents for adjusting the pH and anticakingagents.

Possible surface-active substances are the previously namedsurface-active substances. Preferably the aqueous plant protectionagents according to the invention contain at least one of the previouslynamed anionic surfactants and if necessary one or more nonionicsurfactants, if necessary in combination with a protective colloid. Thequantity of surface-active substances will as a rule be 1 to 50 wt. %,in particular 2 to 30 wt. %, based on the total weight of the aqueousSCs according to the invention. Preferably the surface-active substancesinclude at least one anionic surface-active substance and at least onenonionic surface-active substance, and the proportion of anionic tononionic surface-active substance typically lies in the range from 10:1to 1:10.

Concerning the nature and quantity of the antifoaming agents,thickeners, antifreeze agents and biocides, the same applies asaforesaid.

If necessary, the aqueous SCs according to the invention can containbuffers for pH regulation. Examples of buffers are alkali metal salts ofweak inorganic or organic acids, such as for example phosphoric acid,boric acid, acetic acid, propionic acid, citric acid, fumaric acid,tartaric acid, oxalic acid and succinic acid.

According to a second preferred embodiment, the liquid phase consists ofnon-aqueous organic solvents in which the solubility of the form A, B, Cand/or D, preferably form C, of compound of formula (I) at 25° C. and1013 mbar is not more than 1 wt. %, in particular not more than 0.1 wt.%, and especially not more than 0.01 wt. %. These include in particularaliphatic and cycloaliphatic hydrocarbons and oils, in particular thoseof plant origin, and also C₁-C₄ alkyl esters of saturated or unsaturatedfatty acids or fatty acid mixtures, in particular the methyl esters, forexample methyl oleate, methyl stearate and rape oil methyl ester, butalso paraffinic mineral oils and the like.

Accordingly, the present invention relates also to agents for plantprotection in the form of a non-aqueous suspension concentrate, whichwill also be referred to below as OD (oil-dispersion). Such ODs containthe form A, B, C and/or D, preferably form C, of compound of formula (I)in a finely divided particulate form, wherein the particles of the formA, B, C and/or D, preferably form C, are present suspended in anon-aqueous phase. The size of the active substance particles, i.e. thesize which 90 wt. % of the active substance particles do not exceed,here typically lies below 30 μm, in particular below 20 μm.

Advantageously, in the non-aqueous suspension concentrates, at least 40wt. % and in particular at least 60 wt. % of the particles havediameters below 2 μm.

In such ODs, the quantity of active substance, i.e. the total quantityof compound of formula (I) and of other active substances if necessary,usually lies in the range from 5 to 70 wt. %, in particular in the rangefrom 10 to 50 wt. %, based on the total weight of the non-aqueoussuspension concentrate.

In addition to the active substance and the liquid carrier, non-aqueoussuspension concentrates typically contain surface-active substances, andalso if necessary antifoaming agents, agents to modify the rheology andstabilizers (biocides).

Possible surface-active substances are preferably the previously namedanionic and nonionic surfactants. The quantity of surface-activesubstances will as a rule be 1 to 30 wt. %, in particular 2 to 20 wt. %,based on the total weight of the non-aqueous SCs according to theinvention. Preferably the surface-active substances include at least oneanionic surface-active substance and at least one nonionicsurface-active substance, and the proportion of anionic to nonionicsurface-active substance typically lies in the range from 10:1 to 1:10.

The form A, B, C and/or D, preferably form C, of compound of formula (I)according to the invention can also be formulated as solid plantprotection agents. These include powder, scattering and dusting agentsbut also water-dispersible powders and granules, for example coated,impregnated and homogenous granules. Such formulations can be producedby mixing or simultaneous grinding of the form A, B, C and/or D,preferably form C, of compound of formula (I) with a solid carrier andif necessary other additives, in particular surface-active substances.Granules can be produced by binding of the active substances to solidcarriers. Solid carriers are mineral earths such as silicic acids,silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium and magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, ureas and plant productssuch as cereal flour, tree bark, wood and nutshell flour, cellulosepowder or other solid carriers. Solid formulations can also be producedby spray drying, if necessary in the presence of polymeric or inorganicdrying aids, and if necessary in the presence of solid carriers.

For the production of solid formulations of compounds of formula (I) inform A, B, C and/or D, preferably form C, extrusion processes, fluidizedbed granulation, spray granulation and comparable technologies aresuitable.

Possible surface-active substances are the previously named surfactantsand protective colloids. The quantity of surface-active substances willas a rule be 1 to 30 wt. %, in particular 2 to 20 wt. %, based on thetotal weight of the solid formulation according to the invention.

In such solid formulations, the quantity of active substance, i.e. thetotal quantity of compound of formula (I) and of other active substancesif necessary, usually lies in the range from 5 to 70 wt. %, inparticular in the range from 10 to 50 wt. %, based on the total weightof the solid formulation.

Examples for agrochemical composition types (i.e. formulation examples)and their preparation are:

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention and 5-15 wt %wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/orin a water-soluble solvent (e.g. alcohols) ad 100 wt %. The activesubstance dissolves upon dilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention and 1-10 wt %dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent(e.g. cyclohexanone) ad 100 wt %. Dilution with water gives adispersion.

iii) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of form A, B, C and/or D,preferably form C, or a herbicidal composition comprising at least onecompound of formula (I) in form A, B, C and/or D (component A),preferably form C, and at least one further compound selected from theherbicidal compounds B (component B) and safeners C (component C)according to the invention are comminuted with addition of 2-10 wt %dispersants and wetting agents (e.g. sodium lignosulfonate and alcoholethoxylate), 0.1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water givesa stable suspension of the active substance. For FS type composition upto 40 wt % binder (e.g. polyvinylalcohol) is added.

iv) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50-80 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention are ground finelywith addition of dispersants and wetting agents (e.g. sodiumlignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared aswater-dispersible or water-soluble granules by means of technicalappliances (e. g. extrusion, spray tower, fluidized bed). Dilution withwater gives a stable dispersion or solution of the active substance.

v) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

50-80 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention are ground in arotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodiumlignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate) andsolid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives astable dispersion or solution of the active substance.

vi) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % of form A, B, C and/or D, preferablyform C, or a herbicidal composition comprising at least one compound offormula (I) in form A, B, C and/or D (component A), preferably form C,and at least one further compound selected from the herbicidal compoundsB (component B) and safeners C (component C) according to the inventionare comminuted with addition of 3-10 wt % dispersants (e.g. sodiumlignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) andwater ad 100 wt % to give a fine suspension of the active substance.Dilution with water gives a stable suspension of the active substance.

vii) Microcapsules (CS)

An oil phase comprising 5-50 wt % of form A, B, C and/or D, preferablyform C, or a herbicidal composition comprising at least one compound offormula (I) form A, B, C and/or D (component A), preferably form C, andat least one further compound selected from the herbicidal compounds B(component B) and safeners C (component C) according to the invention,0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon),2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acidand a di- or triacrylate) are dispersed into an aqueous solution of aprotective colloid (e.g. polyvinyl alcohol). Radical polymerizationinitiated by a radical initiator results in the formation ofpoly(meth)acrylate microcapsules. Alternatively, an oil phase comprising5-50 wt % of form A or B according to the invention, 0-40 wt % waterinsoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanatemonomer (e.g. diphenylmethene-4,4′-diisocyanate) are dispersed into anaqueous solution of a protective colloid (e.g. polyvinyl alcohol). Theaddition of a polyamine (e.g. hexamethylenediamine) results in theformation of polyurea microcapsules. The monomers amount to 1-10 wt %.The wt % relate to the total CS composition.

iix) Dustable Powders (DP, DS)

1-10 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention are ground finelyand mixed intimately with solid carrier (e.g. finely divided kaolin) ad100 wt %.

ix) Granules (GR, FG)

0.5-30 wt % of form A, B, C and/or D, preferably form C, or a herbicidalcomposition comprising at least one compound of formula (I) in form A,B, C and/or D (component A), preferably form C, and at least one furthercompound selected from the herbicidal compounds B (component B) andsafeners C (component C) according to the invention is ground finely andassociated with solid carrier (e.g. silicate) ad 100 wt %. Granulationis achieved by extrusion, spray-drying or the fluidized bed.

The agrochemical compositions types i) to ix) may optionally comprisefurther auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt %anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt %colorants.

The application of the form A, B, C and/or D, preferably form C, or theherbicidal agents containing them is effected, if the formulation is notalready ready for use, in the form of aqueous spray fluids. These areprepared by dilution of the aforesaid formulations containing the formA, B, C and/or D, preferably form C, with water. The spray fluids canalso contain other components in dissolved, emulsified or suspendedform, for example fertilizers, active substances of other herbicidal orgrowth-regulating active substance groups, other active substances, forexample active substances for combating animal pests or phyto-pathogenicfungi or bacteria, and also mineral salts which are used for theelimination of nutritional and trace element deficiencies, andnon-phytotoxic oils and oil concentrates. As a rule, these componentsare added to the spray fluid before, during or after the dilution of theformulations according to the invention.

The application of the form A, B, C and/or D, preferably form C, or ofthe plant protection agents containing them can be effected in apre-emergence or in a post-emergence method. If compound of formula (I)is less tolerable for certain crop plants, application techniques can beused wherein the herbicidal agents are sprayed using the sprayingequipment in such a manner that the leaves of the sensitive crop plantsare as far as possible not hit, while the active substances reach theleaves of undesired plants growing under them or the uncovered soilsurface (post-directed, lay-by).

The quantities of compound of formula (I) applied are 0.001 to 3.0 kgactive substance per hectare, preferably 0.005 to 0.25 kg activesubstance (a.s.)/ha, depending on the treatment aim, season, targetplants and growth stage.

In a further embodiment, the application of the form A, B, C and/or D,preferably form C, or the plant protection agent containing them can beeffected by treatment of seed.

Treatment of seed essentially includes all techniques with which theperson skilled in the art is familiar (seed dressing, seed coating, seeddusting, seed soaking, seed film coating, seed multilayer coating, seedencrusting, seed dripping and seed pelleting) on the basis of compoundof formula (I) in form A, B, C and/or D, preferably form C, or agentsprepared therefrom. Here the plant protection agents can be applieddiluted or undiluted.

The term seed includes seed of all types, for example grains, seeds,fruits, tubers, cuttings and similar forms. Preferably, the term seedhere describes grains and seeds.

As seed, seed of the crop plants mentioned above but also the seeds oftransgenic plants or those obtained by conventional breeding methods canbe used.

For the seed treatment, compound of formula (I) in form A, B, C and/orD, preferably form C, is normally used in quantities of 0.001 to 10 kgper 100 kg of seed.

The following illustrations and examples serve to illustrate theinvention and should not be regarded as limiting.

FIG. 1 shows an X-ray powder diffraction diagram of form A. The X-raydiffraction diagram of form A was recorded with a Panalytical X'Pert Prodiffractometer (manufacturer: Panalytical) in reflection geometry(Bragg-Brantano) in the range from 2θ=3°-40° with increments of e.g.0.017° and measurement time of 20 s/step using using Cu-Kα radiation(1.54178 Å) at 25° C. The tube voltage was 45 kV and current 40 mA. Thesample was placed in a silicon single crystal sample holder of 0.2 mmdepth and flattened.

FIG. 2 shows an X-ray powder diffraction diagram of form B. The X-raydiffraction diagram was recorded under the conditions stated for FIG. 1.

FIG. 3 shows an X-ray powder diffraction diagram of form C. The X-raydiffraction diagram was recorded under the conditions stated for FIG. 1.

FIG. 4 shows an X-ray powder diffraction diagram of form C. The X-raydiffraction diagram was recorded under the conditions stated for FIG. 1.

The melting points were determined using DSC with a Mettler Toledo DSC823e/700/229 module. The samples were placed in aluminum standard pans.The sample size in each case was 1 to 10 mg. The heating rate was 10°C./min. The samples were purged with a stream of nitrogen during theexperiment. The melting point was determined as the extrapolated peakonset temperature (also called onset temperature) defined by the pointof intersection of the tangent at the half height of the melting peak,on the principal side of the peak with the linelarily extrapolatedinitial base line.

Single crystal X-ray diffraction: X-ray diffraction data were collectedon a Bruker AXS 8D Pro-spector diffractometer at 100 K with Cu-Kαradiation (1.5418 Å). The images were processed with Saint (Bruker AXS)and the structure was solved with SHELXS and refined with SHELXL.

A PREPARATION EXAMPLES

The preparation of the compound of formula (I) and its forms A, B, C andD is illustrated by the following examples;

Example 1 Ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

Example 1 Step 1: Ethyl2-[[3-[(6-azido-3-chloro-5-fluoro-2-pyridyl)oxy]-2-pyridyl]oxy]acetate

To a solution of 1.8 g (10.78 mmol) 3-chloro-2,5,6-trifluoropyridine(CAS 2879-42-7) in 20 mL DMSO at room temperature was added 0.77 g (11.8mmol) sodium azide and the mixture was stirred 3 hours at roomtemperature. Then a suspension of 2.2 g (11.3 mmol) ethyl2-[(3-hydroxy-2-pyridyl)oxy]acetate (CAS: 353292-81-6) and 7 g (21.5mmol) Cs₂CO₃ in 10 mL DMSO was added to the above mixture in portions.The resulting mixture was stirred at room temperature for 15 hours,diluted with water and extracted with ethyl acetate. The combinedorganic layer was washed with brine, dried over anhydrous Na₂SO₄,filtered and the solvent was removed under reduced pressure. The crudetitle product was used without further purification in the next step.

Example 1 Step 2: Ethyl2-[[3-[(6-amino-3-chloro-5-fluoro-2-pyridyl)oxy]-2-pyridyl]oxy]acetate

To a suspension of 4.8 g (13 mmol) of compound 1 step 1 and 4.3 g (66mmol) zinc in 100 mL THE was added dropwise 50 mL semi-saturated aqueousNH₄Cl solution at 0° C. The mixture was stirred at room temperature for5 hours, filtered and the filter cake was washed with ethyl acetate. Tothe filtrate was added 200 mL water, the mixture was extracted withethyl acetate, the organic layer was dried over anhydrous Na₂SO₄,filtered and the solvent was removed under reduced pressure. The crudeproduct was purified by column chromatography on silica (petrolether/ethyl acetate) to give 2.7 g (8 mmol, 61%) of the desired titleproduct.

¹H-NMR (CDCl₃, ppm): 7.9 (dd, J=4.89 Hz, J=1.51 Hz, 1H); 7.4 (d, J=7.39Hz, 1H); 7.3 (d, J=9.06 Hz, 1H); 6.9 (dd, J=7.65 Hz, J=4.89 Hz, 1H); 4.9(s, 2H); 4.5 (s, 2H); 4.2 (q, J=7.15 Hz, 2H); 1.25 (t, J=7.15 Hz, 3H).

[M+H]=428.1; Rt=1.332 min

Example 1 Step 3:Ethyl(Z)-3-(dimethylcarbamoylamino)-4,4,4-trifluoro-but-2-enoate

To a solution of 104 g (2.73 mol) NaH in 600 mL dry DMF under aN₂-atmosphere was added 233 g (2.18 mol) N,N-dimethylcarbamoyl chloride(CAS: 79-44-7) dissolved in 200 mL dry DMF dropwise over 1 hour at 0-5°C. with stirring. Then 200 g (1.09 mol) ethyl(Z)-3-amino-4,4,4-trifluoro-but-2-enoate (CAS: 372-29-2) dissolved in200 mL dry DMF was added dropwise at a temperature of 0-5° C. over 1hour with stirring. The mixture was stirred at room temperature foranother 2 hours and then poured into ice-water. The mixture wasextracted with ethyl acetate, the combined organic layer was washed withbrine, dried over anhydrous Na₂SO₄, filtered and the solvent was removedunder reduced pressure. The crude product was purified by columnchromatography on silica (petrol ether/ethyl acetate) to give 170 g(0.67 mol, 64%) of the desired product 1 step 3.

Example 1 Step 4: Example 5.2:2-(dimethylamino)-4-(trifluoromethyl)-1,3-oxazin-6-one

To a solution of 170 g (0.67 mol) of compound 1 step 3 in 102 mL POCl₃was added 139 g (0.67 mol) PCl₅ at 0° C. in three portions with 15minutes stirring in between and the mixture was stirred another hour at0° C. The mixture was then stirred at room temperature for another 3hours. The reaction mixture was poured into 250 mL ice water and theprecipitate was collected via filtration and dried to give 84 g (0.40mol, 60%) of the desired product 1 step 4.

¹H-NMR (CDCl₃, ppm): 5.9 (s, 1H); 3.2 (d, J=19.58 Hz, 6H).

[M+H]=209.1; Rt=0.980 min

Example 1 Step 5: Ethyl2-[[3-[[3-chloro-6-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-5-fluoro-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

A solution of 16 g (47 mmol) of compound 1 step 2 and 9.8 g (47 mmol) ofcompound 5.2 in 430 mL glacial acetic acid was stirred at 80° C. for 16hours. Then 9.8 g (47 mmol) of compound 1 step 4 was added and themixture stirred at 80° C. for 16 hours. Again 2.9 g (14 mmol) ofcompound 1 step 4 was added and the mixture stirred at 80° C. for 16hours. Again 9.8 g (47 mmol) of compound 1 step 4 was added and themixture stirred at 80° C. for 16 hours. Then water was added, themixture was extracted with ethyl acetate, the combined organic layer waswashed with water and brine, dried over anhydrous Na₂SO₄, filtered andthe solvent was removed under reduced pressure. The crude product 1 step5 (23 g, 46 mmol, 97%) was used in the next step without furtherpurification.

Example 1 Step 6: Ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

To a solution of 23 g (46 mmol) of the crude compound 1 step 5 in 500 mLDMF was added 38 g (275 mmol) K₂CO₃ followed by 26.6 g (187 mmol) methyliodide at 0° C. The reaction mixture was stirred at room temperature for16 hours, then 38 g (275 mmol) K₂CO₃ was added again followed by 26.6 g(187 mmol) methyl iodide and the mixture was again stirred at roomtemperature for 48 hours. The mixture was poured into water, extractedwith ethyl acetate, the combined organic layer was washed with water andbrine, dried over anhydrous Na₂SO₄, filtered and the solvent was removedunder reduced pressure. The crude product was purified by reversed phasepreparative HPLC (acetonitrile/water containing trifluoroacetic acid) togive 10.3 g (19.9 mmol, 43%) of the desired compound 1 ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate.

¹H-NMR (CDCl₃, ppm): 7.96 (d, J=3.97 Hz, 1H); 7.76 (d, J=7.50 Hz, 1H);7.49 (d, J=7.06 Hz, 1H); 6.95 (dd, J=7.50 Hz, J=5.29 Hz, 1H); 6.26 (s,1H) 4.79 (s, 2H); 4.19 (q, J=7.06 Hz, 2H); 3.48 (s, 3H); 1.24 (t, J=7.06Hz, 3H).

[M+H]=519.0; Rt=1.183 min

Example 2: Preparation of Form a of Compound of Formula (I)

100 mg amorphous compound of formula (I) was dissolved in 1 mL2-propanole. After about 30 min, a crystalline precipitate was obtained,isolated and characterized by PXRD (powder X-ray powder diffractometry),TG (thermogravimetry) and DSC (differential scanning calorimetry).

On the basis of the characteristic reflections, form A was identified.

Example 3: Preparation of Form B of Compound of Formula (I)

23.88 g amorphous compound of formula (I) was dissolved in 20 mL2-propanole. After 90 min a clear brown solution was observed, after 100min the solution turned turbid, some precipitate was obtained. Thesuspension was stirred for 22 h, then the solvent was evaporated usingrotary evaporator. 17.58 g of a white solid were obtained, which wascharacterized by PXRD, TG and DSC.

On the basis of the characteristic reflections, form B was identified.

Example 3: Preparation of Form C of Compound of Formula (I)

84 mL 2PrOH were added to 8.40 g amorphous compound of formula (I) andthe content was stirred overnight. Some precipitate was obtained, whichwas filtered and washed with 5 mL 2-propanole. The solid was dried usingrotary evaporator and 5.50 g of a white solid were obtained, which wascharacterized by PXRD, TG and DSC.

On the basis of the characteristic reflections, form C was identified.

Example 4: Preparation of Form D of Compound of Formula (I)

70 mL 2PrOH were added to 11.2 g amorphous compound of formula (I), themixture was stirred overnight (precipitate). The suspension was filteredand the solid material was dried using a rotary evaporator. 8.5 g of awhite solid were obtained, which was characterized by PXRD, TG and DSC.

On the basis of the characteristic reflections, form D was identified.

The invention claimed is:
 1. A crystalline form C of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,which in an X-ray powder diffraction diagram at 25° C. and Cu-Kαradiation displays at least 3 of the following reflections, quoted as °2θ values: 10.6±0.2, 12.3±0.2, 15.3±0.2, 15.8±0.2, 18.3±0.2, 18.6±0.2,19.2±0.2, 19.9±0.2, 20.6±0.2, 20.9±0.2, 21.8±0.2, 22.6±0.2, 24.5±0.2,25.5±0.2, 26.0±0.2, 27.0±0.2 and 28.3±0.2.
 2. The crystalline form C asclaimed in claim 1 with a content of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetateof at least 94 wt. %.
 3. Ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetateconsisting of at least 90 wt. % of the crystalline form C.
 4. Theprocess for production of the crystalline form C as claimed in claim 1,comprising: i) preparation of a solution of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetatein a solvent which is selected from the group consisting of aliphatichydrocarbons, aromatic hydrocarbons, esters, ketones and alcohols; ii)effecting a crystallization of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate.5. A crystalline form A of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,which in an X-ray powder diffraction diagram at 25° C. and Cu-Kαradiation displays at least 3 of the following reflections, quoted as °2θ values: 4.7±0.2, 7.5±0.2, 9.5±0.2, 12.2±0.2, 12.9±0.2, 13.7±0.2,14.3±0.2, 14.5±0.2, 19.3±0.2, 20.1±0.2 and 24.7±0.2.
 6. A crystallineform B of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,which in an X-ray powder diffraction diagram at 25° C. and Cu-Kαradiation displays at least 3 of the following reflections, quoted as °2θ values: 7.1±0.2, 9.4±0.2, 9.8±0.2, 11.6±0.2, 13.6±0.2, 13.9±0.2,15.3±0.2, 18.3±0.2, 19.0±0.2, 20.0±0.2, 20.8±0.2, 21.6±0.2, 22.3±0.2,24.5±0.2 and 27.2±0.2.
 7. A crystalline form D of ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,which in an X-ray powder diffraction diagram at 25° C. and Cu-Kαradiation displays at least 3 of the following reflections, quoted as °2θ values: 5.2±0.2, 6.9±0.2, 10.4±0.2, 14.7±0.2, 18.9±0.2, 20.1±0.2,21.6±0.2, 22.1±0.2, 23.0±0.2 and 24.7±0.2.
 8. A plant protection agentcontaining ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate,which consists of one or more of crystalline forms A, B, C, and D in atleast 90 wt %, and one or more additives customary for the formulationof plant protection agents.
 9. The plant protection agent as claimed inclaim 8 in the form of an aqueous suspension concentrate.
 10. The plantprotection agent as claimed in claim 8 in the form of a non-aqueoussuspension concentrate.
 11. The plant protection agent as claimed inclaim 8 in the form of a powder or granules dispersible in water.
 12. Amethod for combatting undesired plant growth comprising applying toplants, the habitat thereof, or seeds an effective amount of an agentcontaining ethyl2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]pxy]acetate, wherein one or more crystalline forms A, B, C, and D is presentin at least 90 wt %.